Method for Producing Dialkylphosphinic Acids and Esters and Salts Thereof by Means of Allyl Alcohols-Acroleins and use Thereof

ABSTRACT

The invention relates to a method for producing mono-carboxyfunctionalized dialkylphosphinic acids and esters and salts thereof, characterized in that a) a phosphinic acid source (I) is reacted with olefins (IV) to yield an alkylphosphonic acid, salt or ester (II) thereof in the presence of a catalyst A, b) the thus obtained alkyl phosphonic acid, salt, salt or ester (II) thereof is reacted with compounds of formula (V) and/or (VI′) to yield mono-functionalized dialkylphosphinic acid derivatives (VI) and/or (VI′) in the presence of a catalyst B, and c) the thus obtained mono-functionalized dialkylphosphinic acid derivatives (VI) and/or (VI′) are reacted to yield a mono-carboxyfunctionalized dialkylphosphinic acid derivative (III) in the presence of a catalyst C, wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7  are the same or different and stand independently of each other, among other things, for H 1  C 1 -C 18  alkyl, C 6 -C 18  aryl, C 6 -C 18  aralkyl, C 6 -C 18  alkylaryl, and X and Y are the same or different and stand independently of each other for H, C 1 -C 18  alkyl, C 6 -C 18  aryl, C 6 -C 18  aralkyl, C 6 -C 18  alkylaryl, Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Cu, Ni, Li, Na, K and/or a protonized nitrogen base, and the catalysts A and C are formed by transition metals and/or transition metal compounds and/or catalyst systems composed of a transition metal and/or a transition metal compound and at least one ligand, and catalyst B is formed by compounds forming peroxides and/or peroxo compounds and/or azo compounds and/or alkali metals and/or alkaline earth metals, alkali hydrides, alkaline earth hydrides and/or alkali alcoholates and alkaline earth alcoholates.

This invention relates to a method for producing dialkylphosphinicacids, esters and salts and also to their use.

There are certain dialkylphosphinic acids, known asmonocarboxy-functionalized dialkylphosphinic acids, as hereinbelowdefined, of which hitherto very substantially only the esters areavailable. The latter are obtainable via multiple steps proceeding fromphosphonous dihalides. These include reaction of dihalophosphines withactivated olefinic compounds such as acrylic acid followed by theesterification with alcohols of the acid chloride and anhydridederivatives initially formed (V. K. Khairuilin, R. R. Shagidullin, Zh.Obshch. Khim, 36, 289-296).

Dialkylphosphinic acids for the purposes of the present invention arethus always monocarboxy-functionalized dialkylphosphinic acids evenwhere this is not expressly mentioned. This definition includes thecorresponding esters and salts.

Such dialkylphosphinic esters are also obtained on adding phosphonousesters onto α,β-unsaturated carboxylic esters in the presence ofperoxidic catalysts (Houben-Weyl, volume 1211, pages 258-259). Thephosphonous esters themselves are prepared from phosphonous dihalides byreaction with alcohols, or hydrolysis, and subsequent esterification.The aforementioned phosphonous dihalides themselves are prepared in acostly and inconvenient synthesis from phosphoryl trichloride and alkylchloride in the presence of aluminum chloride (Houben-Weyl, volume 1211,page 306). The reaction is strongly exothermic and difficult to controlon an industrial scale. In addition, the reaction by-produces variousproducts which, like some of the aforementioned starting materials also,are toxic and/or corrosive, i.e., extremely undesirable (particularlysince the products are not obtainable free of halogen).

A further method for producing monocarboxy-functionalizeddialkylphosphinic esters is based on the reaction of yellow phosphoruswith methyl chloride to form methylphosphonous acid which is thenesterified and thereafter reacted with acrylic ester (DE-A-101 53 780).

Monocarboxy-functionalized dialkylphosphinic esters are also obtainableby reaction of bis(trimethylsilyl) phosphonite —HP(OSiMe₃)₂— withα,β-unsaturated carboxylic acid components, subsequent alkylation withalkyl halides by the Arbuzov reaction and alcoholysis (Kurdyumova, N.R.; Rozhko, L. F.; Ragulin, V. V.; Tsvetkov, E. N.; Russian Journal ofGeneral Chemistry (Translation of Zhurnal Obshchei Khimii (1997),67(12), 1852-1856). The bis(trimethylsilyl) phosphonite ester isobtained from potassium or ammonium hypophosphite by reaction withhexamethyldisilazane.

Hitherto there are no methods in existence for producingmonocarboxy-functionalized dialkylphosphinic acids, esters and saltsthat are available economically and on a large industrial scale and moreparticularly enable a high space-time yield to be achieved. Nor arethere any methods that are sufficiently effective without unwelcomehalogen compounds as starting materials, nor any where the end productsare easy to obtain or isolate or obtainable in a specific and desirablemanner under controlled reaction conditions (such as atransesterification for example).

We have found that this object is achieved by a method for producingmonocarboxy-functionalized dialkylphosphinic acids, esters and salts,which comprises

a) reacting a phosphinic acid source (I)

with olefins (IV)

in the presence of a catalyst A to form an alkylphosphonous acid, saltor ester (II)

b) reacting the resulting alkylphosphonous acid, salt or ester (II) withan allyl alcohol (V) and/or acrolein (V′)

in the presence of a catalyst B to form the monofunctionalizeddialkylphosphinic acid derivative (VI) and/or (VI′)

andc) reacting the monofunctionalized dialkylphosphinic acid derivative(VI) and or (VI′) with an oxidizing agent or with an oxidizing agent andwater or in the presence of a catalyst C with oxygen and water to formthe monocarboxy-functionalized dialkylphosphinic acid derivative (III)

where R¹, R², R³, R⁴, R⁵, R⁶, R⁷ are identical or different and are eachindependently H, C₁-C₁₈-alkyl, C₆-C₁₈-aryl, C₆-C₁₈-aralkyl,C₆-C₁₈-alkylaryl, CN, CHO, OC(O)CH₂CN, CH(OH)C₁H₅, CH₂CH(OH)CH₃,9-anthracene, 2-pyrrolidone, (CH₂)_(m)OH, (CH₂)_(m)NH₂, (CH₂)_(m)NCS,(CH₂)_(m)NC(S)NH₂, (CH₂)_(m)SH, (CH₂)_(m)S-2-thiazoline, (CH₂)_(m)SiMe₃,C(O)R⁸, (CH₂)_(m)C(O)R⁸, CH═CH—R⁸, CH═CH—(O)R⁸ and where R⁸ isC₁-C₈-alkyl or C₆-C₁₈-aryl and m is an integer from 0 to 10 and X and Yare identical or different and are each independently H, C₁-C₁₈-alkyl,C₆-C₁₈-aryl, C₆-C₁₈-aralkyl, C₆-C₁₈-alkylaryl, (CH₂)_(k)OH,CH₂—CHOH—CH₂OH, (CH₂)_(k)O(CH₂)_(k)H, (CH₂)_(k)—H(OH)—(CH₂)_(k)H,(CH₂—CH₂O)_(k)H, (CH₂—C[CH₃]HO)_(k)H, (CH₂—C[CH₃]HO)_(k)(CH₂—CH₂O)_(k)H,(CH₂—CH₂O)_(k)(CH₂—C[CH₃]HO)H, (CH₂—CH₂O)_(k)-alkyl,(CH₂—C[CH₃]HO)_(k)-alkyl, (CH₂— [CH₃]HO)_(k)(CH₂—CH₂O)_(k)-alkyl,(CH₂—CH₂O)_(k)(CH₂—C[CH₃]HO)O-alkyl, (CH₂)_(k)—H═CH(CH₂)_(k)H,(CH₂)_(k)NH₂, (CH₂)_(k)N[(CH₂)_(k)H]₂, where k is an integer from 0 to10, and/or Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Cu,Ni, Li, Na, K, H and/or a protonated nitrogen base and the catalysts Aand C comprise transition metals and/or transition metal compoundsand/or catalyst systems composed of a transition metal and/or transitionmetal compound and at least one ligand, and the catalyst B comprisesperoxide-forming compounds and/or peroxo compounds and/or comprises azocompounds and/or comprises alkali metals and/or alkaline earth metals,hydrides and/or alkoxides.

Preferably, the monocarboxy-functionalized dialkylphosphinic acid, itssalt or ester (III) obtained after step c) is subsequently reacted in astep d) with metal compounds of Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn,Ce, Bi, Sr, Mn, Li, Na, K and/or a protonated nitrogen base to form thecorresponding monocarboxy-functionalized dialkylphosphinic acid salts(III) of these metals and/or of a nitrogen compound.

Preferably, the alkylphosphonous acid, salt or ester (II) obtained afterstep a) and/or the monofunctionalized dialkylphosphinic acid, salt orester (VI) and/or (VI′) obtained after step b) and/or themonocarboxy-functionalized dialkylphosphinic acid, salt or ester (III)obtained after step c) and/or the particular resulting reaction solutionthereof are esterified with an alkylene oxide or an alcohol M-OH and/orM′-OH, and the respectively resulting alkylphosphonous ester (II),monofunctionalized dialkylphosphinic ester (VI) and/or (VI') and/ormonocarboxy-functionalized dialkylphosphinic ester (III) are subjectedto the further reaction steps b), c) or d).

Preferably, the groups C₅-C₁₈-aryl, C₆-C₁₈-aralkyl and C₆-C₁₅-alkylarylare substituted with SO₃X₂, —C(O)CH₃, OH, CH₂OH, CH₃SO₃X₂, PO₃X₂, NH₂,NO₂, OCH₃, SH and/or OC(O)CH₃.

Preferably, R¹, R², R³, R⁴, R⁵, R⁶, R⁷ are identical or different andare each independently H, methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl, tert-butyl and/or phenyl.

Preferably, X and Y are identical or different and are each H, Ca, Mg,Al, Zn, Ti, Fe, Ce, methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl, fed-butyl, phenyl, ethylene glycol, propyl glycol, butylglycol, pentyl glycol, hexyl glycol, allyl and/or glycerol.

Preferably m=1 to 10 and k=2 to 10.

Preferably, the catalyst system A or C respectively is formed byreaction of a transition metal and/or of a transition metal compound andat least one ligand.

Preferably, the transition metals and/or transition metal compoundscomprise such from the first, seventh and eighth transition groups.

Preferably, the transition metals and/or transition metal compoundscomprise rhodium, nickel, palladium, platinum, ruthenium and/or gold.

Preferably, the catalyst B comprises hydrogen peroxide, sodium peroxide,lithium peroxide, potassium persulfate, sodium persulfate, ammoniumpersulfate, sodium peroxodisulfate, potassium peroxoborate, peraceticacid, benzoyl peroxide, di-t-butyl peroxide and/or peroxodisulfuric acidand/or comprises azobisisobutyronitrile, 2,2′-azobis(2-amidinopropane)dihydrochloride and/or 2,2′azobis(N,N′ dimethylene-isobutyramidine)dihydrochloride and/or comprises lithium, lithium hydride, lithiumaluminum hydride, methyllithium, butyllithium, t-butyllithium, lithiumdiisopropylamide, sodium, sodium hydride, sodium borohydride, sodiummethoxide, sodium ethoxide, sodium butoxide, potassium methoxide,potassium ethoxide and/or potassium butoxide.

Preferably, the allyl alcohols (V) comprise 2-propen-1-ol,2-methyl-2-propen-1-ol, 2-isobutyl-2-propen-1-ol,2-(trimethylsilyl)-2-propen-1-ol, 3-phenyl-2-propen-1-ol,3-(trimethylsilyl)-2-propen-1-ol,3-(4-hydroxy-3-methoxyphenyl)-2-propen-1-ol,2-methyl-3-phenyl-2-propen-1-ol, 2-buten-1-ol, 2-methyl-2-buten-1-ol,3-(trimethylsilyl)-2-buten-1-ol, 3-methyl-2-buten-1-ol,3-phenyl-2-buten-1-ol, 3-(trimethylsilyl)-2-buten-1-ol,2-methyl-3-phenyl-2-buten-1-ol, 2-penten-1-ol, 2-methyl-2-penten-1-ol,2-(trimethylsilyl)-2-penten-1-ol, 3-methyl-2-penten-1-ol,3-phenyl-2-penten-1-ol, 4-methyl-2-penten-1-ol and/or4-phenyl-2-penten-1-ol.

Preferably, the acroleins (V′) comprise 2-propenal, 2-methyl-2-propenal,2-phenyl-2-propenal, 3-phenyl-2-propenal, 2-methyl-3-phenyl-2-propenal,2-butenal, 2-methyl-2-butenal, 2-phenyl-2-butenal, 3-methyl-2-butenal,2-methyl-2-butenal, 2-pentenal, 2-methyl-2-pentenal,2-phenyl-2-pentenal, 4-methyl-2-phenyl-2-pentenal and/or2,2-dimethyl-4-pentenal.

Preferably, the alcohol of the general formula M-OH comprises linear orbranched, saturated and unsaturated, monohydric organic alcohols havinga carbon chain length of C₁-C₁₈ and the alcohol of the general formulaM′-OH comprises linear or branched, saturated and unsaturated polyhydricorganic alcohols having a carbon chain length of C₁-C₁₈.

The present invention additionally provides for the use ofmonocarboxy-functionalized dialkylphosphinic acids, salts and estersobtained according to one or more of claims 1 to 13 as an intermediatefor further syntheses, as a binder, as a crosslinker or accelerate tocure epoxy resins, polyurethanes and unsaturated polyester resins, aspolymer stabilizers, as crop protection agents, as a therapeutic oradditive in therapeutics for humans and animals, as a sequestrant, as amineral oil additive, as a corrosion-control agent, in washing andcleaning applications and in electronic applications.

The present invention likewise provides for the use ofmonocarboxy-functionalized dialkylphosphinic acids, salts and esters(III) obtained according to one or more of claims 1 to 13 as a flameretardant, more particularly as a flame retardant for clearcoats andintumescent coatings, as a flame retardant for wood and other cellulosicproducts, as a reactive and/or nonreactive flame retardant for polymers,in the manufacture of flame-retardant polymeric molding materials, inthe manufacture of flame-retardant polymeric molded articles and/or forflame-retardant finishing of polyester and cellulose straight and blendfabrics by impregnation.

The present invention also provides a flame-retardant thermoplastic orthermoset polymeric molding material containing 0.5% to 45% by weight ofmonocarboxy-functionalized dialkylphosphinic acids, salts or esters(III) obtained according to one or more of claims 1 to 13, 0.5% to 95%by weight of thermoplastic or thermoset polymer or mixtures thereof, 0%to 55% by weight of additives and 0% to 55% by weight of filler orreinforcing materials, wherein the sum total of the components is 100%by weight.

Lastly, the invention also provides flame-retardant thermoplastic orthermoset polymeric molded articles, films, threads and fiberscontaining 0.5% to 45% by weight of monocarboxy-functionalizeddialkylphosphinic acids, salts or esters (III) obtained according to oneor more of claims 1 to 13, 0.5% to 95% by weight of thermoplastic orthermoset polymer or mixtures thereof, 0% to 55% by weight of additivesand 0% to 55% by weight of filler or reinforcing materials, wherein thesum total of the components is 100% by weight.

All the aforementioned reactions can also be carried out in stages;similarly, the various processing steps can also utilize the respectiveresulting reaction solutions.

When the monocarboxy-functionalized dialkylphosphinic acid (III) afterstep d) comprises an ester, an acidic or basic hydrolysis may preferablybe carried out in order that the free monocarboxy-functionalizeddialkylphosphinic acid or salt may be obtained.

Preferably, the monocarboxy-functionalized dialkylphosphinic acidcomprises 3-(ethylhydroxyphosphinyl)propionic acid,3-(propylhydroxyphosphinyl)propionic acid,3-(i-propylhydroxyphosphinyl)propionic acid,3-(butylhydroxyphosphinyl)-propionic acid,3-(sec-butylhydroxyphosphinyl)propionic acid,3-(1-butyl-hydroxyphosphinyl)propionic acid,3-(2-phenylethylhydroxyphosphinyl)propionic acid,3-(ethylhydroxyphosphinyl)-2-methylpropionic acid,3-(propylhydroxyphos-phinyl)-2-methylpropionic acid,3-(i-propylhydroxyphosphinyl)-2-methylpropionic acid,3-(butylhydroxyphosphinyl)-2-methylpropionic acid,3-(sec-butylhydroxy-phosphinyl)-2-methylpropionic acid,3-(1-butylhydroxyphosphinyl)-2-methylpropionic acid,3-(2-phenylethylhydroxyphosphinyi)-2-methylpropionic acid,3-(ethylhydroxyphosphinyl)-3-phenylpropionic acid,3-(propylhydroxyphosphinyl)-3-phenylpropionic acid,3-(i-propylhydroxyphosphinyl)-3-phenylpropionic acid,3-(butylhydroxyphosphinyl)-3-phenylpropionic acid,3-(1-butylhydroxyphosphinyl)-3-phenylpropionic acid,3-(sec-butylhydroxyphosphinyl)-3-phenylpropionic acid,3-(2-phenylethylhydroxyphosphinyl)-3-phenylpropionic acid.

Preferably, the monocarboxy-functionalized dialkylphosphinic estercomprises a propionic acid, methyl, ethyl; i-propyl; butyl, phenyl;2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl and/or2,3-dihydroxypropyl ester of the aforementionedmonocarboxy-functionalized dialkylphosphinic acids or mixtures thereof.

Preferably, the monocarboxy-functionalized dialkylphosphinic saltcomprises an aluminum(III), calcium(II), magnesium(II), cerium(III),titanium(IV) and/or zinc(II) salt of the aforementionedmonocarboxy-functionalized dialkylphosphinic acids or of theaforementioned esters of the monocarboxy-functionalizeddialkylphosphinic acids.

Target compounds also include those esters and salts where theesterification and salt formation, respectively, takes place on thephosphinic acid group (at X in formula (III)) or on the propionic acidgroup (at Y in formula (III)).

Preferably, the transition metals for catalyst A comprise elements ofthe seventh and eighth transition groups (a metal of group 7, 8, 9 or10, in modern nomenclature), for example rhenium, ruthenium, cobalt,rhodium, iridium, nickel, palladium and platinum.

Preference for use as source of the transition metals and transitionmetal compounds is given to their metal salts. Suitable salts are thoseof mineral acids containing the anions fluoride, chloride, bromide,iodide, fluorate, chlorate, bromate, iodate, fluorite, chlorite,bromite, iodite, hypofluorite, hypochlorite, hypobromite, hypoiodite,perfluorate, perchlorate, perbromate, periodate, cyanide, cyanate,nitrate, nitride, nitrite, oxide, hydroxide, borate, sulfate, sulfite,sulfide, persulfate, thiosulfate, sulfamate, phosphate, phosphite,hypophosphite, phosphide, carbonate and sulfonate, for examplemethanesulfonate, chlorosulfonate, fluorosulfonate,trifluoromethanesulfonate, benzenesulfonate, naphthylsulfonate,toluenesulfonate, t-butylsulfonate, 2-hydroxypropanesulfonate andsulfonated ion exchange resins; and/or organic salts, for exampleacetylacetonates and salts of a carboxylic acid having up to 20 carbonatoms, for example formate, acetate, propionate, butyrate, oxalate,stearate and citrate including halogenated carboxylic acids having up to20 carbon atoms, for example trifluoroacetate, trichloroacetate.

A further source of the transition metals and transition metal compoundsis salts of the transition metals with tetraphenylborate and halogenatedtetraphenylborate anions, for example perfluorophenylborate.

Suitable salts similarly include double salts and complex saltsconsisting of one or more transition metal ions and independently one ormore alkali metal, alkaline earth metal, ammonium, organic ammonium,phosphonium and organic phosphonium ions and independently one or moreof the abovementioned anions. Examples of suitable double salts areammonium hexachloropalladate and ammonium tetrachloropalladate.

Preference for use as a source of the transition metals is given to thetransition metal as an element and/or a transition metal compound in itszerovalent state.

Preferably, the transition metal salt is used as a metal, or as an alloywith further metals, in which case boron, zirconium, tantalum, tungsten,rhenium, cobalt, iridium, nickel, palladium, platinum and/or gold ispreferred here. The transition metal content in the alloy used ispreferably 45-99.95% by weight.

Preferably, the transition metal is used in microdisperse form (particlesize 0.1 mm-100 μm).

Preferably, the transition metal is used supported on a metal oxide suchas, for example, alumina, silica, titanium dioxide, zirconium dioxide,zinc oxide, nickel oxide, vandium oxide, chromium oxide, magnesiumoxide, Celite®, diatomaceous earth, on a metal carbonate such as, forexample, barium carbonate, calcium carbonate, strontium carbonate, on ametal sulfate such as, for example, barium sulfate, calcium sulfate,strontium sulfate, on a metal phosphate such as, for example, aluminumphosphate, vanadium phosphate, on a metal carbide such as, for example,silicone carbide, on a metal aluminate such as, for example, calciumaluminate, on a metal silicate such as, for example, aluminum silicate,chalks, zeolites, bentonite, montmorillonite, hectorite, onfunctionalized silicates, functionalized silica gels such as, forexample, SiliaBond®, QuadraSil™, on functionalized polysiloxanes suchas, for example, Deloxan®, on a metal nitride, on carbon, activatedcarbon, mullite, bauxite, antimonite, scheelite, perovskite,hydrotalcite, heteropolyanions, on functionalized and unfunctionalizedcellulose, chitosan, keratin, heteropolyanions, on ion exchangers suchas, for example, Amberlite™, Amberjet™, Ambersep™, Dowex®, Lewatit®,ScavNet®, on functionalized polymers such as, for example, Chelex®,Quadrapure™, Smopex®, PolyOrgs®, on polymer-bound phosphanes, phosphaneoxides, phosphinates, phosphonates, phosphates, amines, ammonium salts,amides, thioamides, ureas, thioureas, triazines, imidazoles, pyrazoles,pyridines, pyrimidines, pyrazines, thiols, thiol ethers, thiol esters,alcohols, alkoxides, ethers, esters, carboxylic acids, acetates,acetals, peptides, hetarenes, polyethyleneimine/silica and/ordendrimers,

Suitable sources for the metal salts and/or transition metals likewisepreferably include their complex compounds. Complex compounds of themetal salts and/or transition metals are composed of the metalsalts/transition metals and one or moe complexing agents. Suitablecomplexing agents include for example olefins, diolefins, nitriles,dinitriles, carbon monoxide, phosphines, diphosphines, phosphites,diphosphites, dibenzylideneacetone, cyclopentadienyl, indenyl orstyrene. Suitable complex compounds of the metal salts and/or transitionmetals may be supported on the abovementioned support materials.

The proportion in which the supported transition metals mentioned arepresent is preferably in the range from 0.01% to 20% by weight, morepreferably from 0.1% to 10% by weight and even more preferably from 0.2%to 5% by weight, based on the total mass of the support material.

Suitable sources for transition metals and transition metal compoundsinclude for example

palladium, platinum, nickel, rhodium; palladium platinum, nickel orrhodium, on alumina, on silica, on barium carbonate, on barium sulfate,on calcium carbonate, on strontium carbonate, on carbon, on activatedcarbon; platinum-palladium-gold alloy, aluminum-nickel alloy,iron-nickel alloy, lanthanide-nickel alloy, zirconium-nickel alloy,platinum-iridium alloy, platinum-rhodium alloy; Raney® nickel,nickel-zinc-iron oxide; palladium(II) chloride, palladium(II) bromide,palladium(II) iodide, palladium(II) fluoride, palladium(II) hydride,palladium(II) oxide, palladium(II) peroxide, palladium(II) cyanide,palladium(II) sulfate, palladium(II) nitrate, palladium(II) phosphide,palladium(II) boride, palladium(II) chromium oxide, palladium(II) cobaltoxide, palladium(II) carbonate hydroxide, palladium(II) cyclohexanebutyrate, palladium(II) hydroxide, palladium(II) molybdate,palladium(II) octanoate, palladium(II) oxalate, palladium(II)perchlorate, palladium(II) phthalocyanine, palladium(II)5,9,14,18,23,27,32,36-octabutoxy-2,3-naphthalocyanine, palladium(II)sulfamate, palladium(II) perchlorate, palladium(II) thiocyanate,palladium(II) bis(2,2,6,6-tetramethyl-3,5-heptanedionate), palladium(II)propionate, palladium(II) acetate, palladium(II) stearate, palladium(II)2-ethylhexanoate, palladium(II) acetylacetonate, palladium(II)hexafluoroacetylacetonate, palladium(II) tetrafluoroborate,palladium(II) thiosulfate, palladium(II) trifluoroacetate, palladium(II)phthalocyaninetetrasulfonic acid tetrasodium salt, palladium(II) methyl,palladium(II) cyclopentadienyl, palladium(II) methylcyclopentadienyl,palladium(II) ethylcyclopentadienyl, palladium(II)pentamethylcyclopentadienyl, palladium(II)2,3,7,8,12,13,17,18-octaethyl-21 H,23H-porphine, palladium(II)5,10,15,20-tetraphenyl-21H,23H-porphine, palladium(II)bis(5-[[4-(dimethylamino)phenyl]imino]-8(5H)-quinolinone), palladium(II)2,11,20,29-tetra-tert-butyl-2,3-naphthalocyanine, palladium(II)2,9,16,23-tetraphenoxy-29H,31H-phthalocyanine, palladium(II)5,10,15,20-tetrakis(pentafluorophenyl)-21H,23H-porphine and the1,4-bis(diphenylphosphine)butane, 1,3-bis(diphenylphosphino)propane,2-(2′-di-tert-butylphosphine)biphenyl, acetonitrile, benzonitrile,ethylenediamine, chloroform, 1,2-bis(phenylsuifinyl)ethane,1,3-bis(2,6-diisopropylphenyl)imidazolidene)(3-chloropyridyl),2′-(dimethylamino)-2-biphenylyl, dinorbornylphosphine,2-(dimethylaminomethyl)ferrocene, allyl, bis(diphenylphosphino)butane,(N-succinimidyl)bis(triphenylphosphine), dimethylphenylphosphine,methyldiphenylphosphine, 1,10-phenanthroline, 1,5-cyclooctadiene,N,N,N′,N′-tetramethylethylenediamine, triphenylphosphine,tri-o-tolylphosphine, tricyclohexylphosphine, tributylphosphine,triethylphosphine, 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl,1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene,1,3-bis(mesityl)imidazol-2-ylidene,1,1′-bis(diphenylphosphino)ferrocene, 1,2-bis(diphenylphosphino)ethane,N-methylimidazole, 2,2′-bipyridine, (bicyclo[2.2.1]hepta-2,5-diene),bis(di-tert-butyl(4-dimethylaminophenyl)phosphine), bis(tert-butylisocyanide), 2-methoxyethyl ether, ethylene glycol dimethyl ether,1,2-dimethoxyethane, bis(1,3-diamino-2-propanol),bis(N,N-diethylethylenediamine), 1,2-diaminocyclohexane, pyridine,2,2′:6′,2″-terpyridine, diethyl sulfide, ethylene and amine complexesthereof;nickel(II) chloride, nickel(II) bromide, nickel(II) iodide, nickel(II)fluoride, nickel(II) hydride, nickel(II) oxide, nickel(II) peroxide,nickel(II) cyanide, nickel(II) sulfate, nickel(II) nitrate, nickel(II)phosphide, nickel(II) boride, nickel(II) chromium oxide, nickel(II)cobalt oxide, nickel(II) carbonate hydroxide, nickel(II) cyclohexanebutyrate, nickel(II) hydroxide, nickel(II) molybdate, nickel(II)octanoate, nickel(II) oxalate, nickel(II) perchlorate, nickel(II)phthalocyanine, nickel(II)5,9,14,18,23,27,32,36-octabutoxy-2,3-naphthalocyanine, nickel(II)sulfamate, nickel(II) perchlorate, nickel(II) thiocyanate, nickel(II)bis(2,2,6,6-tetramethyl-3,5-heptanedionate), nickel(II)propionate,nickel(II) acetate, nickel(II) stearate, nickel(II) 2-ethylhexanoate,nickel(II) acetylacetonate, nickel(II) hexafluoroacetylacetonate,nickel(II) tetrafluoroborate, nickel(II) thiosulfate, nickel(II)trifluoroacetate, nickel(II) phthalocyaninetetrasulfonic acidtetrasodium salt, nickel(II) methyl, nickel(II) cyclopentadienyl,nickel(II) methylcyclopentadienyl, nickel(II) ethylcyclopentadienyl,nickel(II) pentamethylcyclopentadienyl, nickel(II)2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphine, nickel(II)5,10,15,20-tetraphenyl-21H,23H-porphine, nickel(II)bis(5-[[4-(dimethylamino)phenyl]imino]-8(5H)-quinolinone), nickel(II)2,11,20,29-tetra-tert-butyl-2,3-naphthalocyanine, nickel(II)2,9,16,23-tetraphenoxy-29H,31H-phthalocyanine, nickel(II)5,10,15,20-tetrakis(pentafluorophenyl)-21H,23H-porphine and the1,4-bis(diphenylphosphine)butane, 1,3-bis(diphenylphosphino)propane,2-(2′-di-tert-butylphosphine)biphenyl, acetonitrile, benzonitrile,ethylenediamine, chloroform, 1,2-bis(phenylsulfinyl)ethane,1,3-bis(2,6-diisopropylphenyl)imidazolidene)(3-chloropyridyl),2′-(dimethylamino)-2-biphenylyl, dinorbornylphosphine,2-(dimethylaminomethyl)ferrocene, allyl, bis(diphenylphosphino)butane,(N-succinimidyl)bis(triphenylphosphine), dimethylphenylphosphine,methyldiphenylphosphine, 1,10-phenanthroline, 1,5-cyclooctadiene,N,N,N′,N′-tetramethylethylenediamine, triphenylphosphine,tri-o-tolylphosphine, tricyclohexylphosphine, tributylphosphine,triethylphosphine, 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl,1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene,1,3-bis(mesityl)imidazol-2-ylidene,1,1′-bis(diphenylphosphino)ferrocene, 1,2-bis(diphenylphosphino)ethane,N-methylimidazole, 2,2′-bipyridine, (bicyclo[2.2.1]hepta-2,5-diene),bis(di-tert-butyl(4-dimethylaminophenyl)phosphine), bis(tert-butylisocyanide), 2-methoxyethyl ether, ethylene glycol dimethyl ether,1,2-dimethoxyethane, bis(1,3-diamino-2-propanol),bis(N,N-diethylethylenediamine), 12-diaminocyclohexane, pyridine,2,2′:6′,2″-terpyridine, diethyl sulfide, ethylene and amine complexesthereof; platinum(II) chloride, platinum(II) bromide, platinum(II)iodide, platinum(II) fluoride, platinum(II) hydride, platinum(II) oxide,platinum(II) peroxide, platinum(II) cyanide, platinum(II) sulfate,platinum(II) nitrate, platinum(II) phosphide, platinum(II) boride,platinum(II) chromium oxide, platinum(II) cobalt oxide, platinum(II)carbonate hydroxide, platinum(II) cyclohexane butyrate, platinum(II)hydroxide, platinum(II) molybdate, platinum(II) octanoate, platinum(II)oxalate, platinum(II) perchlorate, platinum(II) phthalocyanine,platinum(II) 5,9,14,18,23,27,32,36-octabutoxy-2,3-naphthalocyanine,platinum(II) sulfamate, platinum(II) perchlorate, platinum(II)thiocyanate, platinum(II) bis(2,2,6,6-tetramethyl-3,5-heptanedionate),platinum(II) propionate, platinum(II) acetate, platinum(II) stearate,platinum(II) 2-ethylhexanoate, platinum(II) acetylacetonate,platinum(II) hexafluoroacetylacetonate, platinum(II) tetrafluoroborate,platinum(II) thiosulfate, platinum(II) trifluoroacetate, platinum(II)phthalocyaninetetrasulfonic acid tetrasodium salt, platinum(II) methyl,platinum(II) cyclopentadienyl, platinum(II) methylcyclopentadienyl,platinum(II) ethylcyclopentadienyl, platinum(II)pentamethylcyclopentadienyl, platinum(II)2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphine, platinum(II)5,10,15,20-tetraphenyl-21H,23H-porphine, platinum(II)bis(5-[[4-(dimethylamino)phenyl]imino]-8(5H)-quinolinone), platinum(II)2,11,20,29-tetra-tert-butyl-2,3-naphthalocyanine, platinum(II)2,9,16,23-tetraphenoxy-29H,31H-phthalocyanine, platinum(II)5,10,15,20-tetrakis(pentafluorophenyl)-21H,23H-porphine and the1,4-bis(diphenylphosphine)butane, 1,3-bis(diphenylphosphino)propane,2-(2′-di-tert-butylphosphine)biphenyl, acetonitrile, benzonitrile,ethylenediamine, chloroform, 1,2-bis(phenyl-sulfinyl)ethane,1,3-bis(2,6-diisopropylphenyl)imidazolidene)(3-chloropyridyl),2′-(dimethylamino)-2-biphenylyl, dinorbornylphosphine,2-(dimethylamino-methyl)ferrocene, allyl, bis(diphenylphosphino)butane,(N-succinimidyl)bis-(triphenylphosphine), dimethylphenylphosphine,methyldiphenylphosphine, 1,10-phenanthroline, 1,5-cyclooctadiene,N,N,N′,N′-tetramethylethylenediamine, triphenylphosphine,tri-o-tolylphosphine, tricyclohexylphosphine, tributylphosphine,triethylphosphine, 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl,1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene,1,3-bis(mesityl)imidazol-2-ylidene,1,1′-bis(diphenylphosphino)ferrocene, 1,2-bis(diphenylphosphino)ethane,N-methylimidazole, 2,2′-bipyridine, (bicyclo[2.2.1]hepta-2,5-diene),bis(di-tert-butyl(4-dimethylaminophenyl)phosphine), bis(tert-butylisocyanide), 2-methoxyethyl ether, ethylene glycol dimethyl ether,1,2-dimethoxyethane, bis(1,3-diamino-2-propanol),bis(N,N-diethylethylenediamine), 12-diaminocyclohexane, pyridine,2,2′:6′,2″-terpyridine, diethyl sulfide, ethylene and amine complexesthereof;rhodium chloride, rhodium bromide, rhodium iodide, rhodium fluoride,rhodium hydride, rhodium oxide, rhodium peroxide, rhodium cyanide,rhodium sulfate, rhodium nitrate, rhodium phosphide, rhodium boride,rhodium chromium oxide, rhodium cobalt oxide, rhodium carbonatehydroxide, rhodium cyclohexane butyrate, rhodium hydroxide, rhodiummolybdate, rhodium octanoate, rhodium oxalate, rhodium perchlorate,rhodium phthalocyanine, rhodium5,9,14,18,23,27,32,36-octabutoxy-2,3-naphthalocyanine, rhodiumsulfamate, rhodium perchlorate, rhodium thiocyanate, rhodiumbis(2,2,6,6-tetramethyl-3,5-heptanedionate), rhodium propionate, rhodiumacetate, rhodium stearate, rhodium 2-ethylhexanoate, rhodiumacetylacetonate, rhodium hexafluoroacetylacetonate, rhodiumtetrafluoroborate, rhodium thiosulfate, rhodium trifluoroacetate,rhodium phthalocyaninetetrasulfonic acid tetrasodium salt, rhodiummethyl, rhodium cyclopentadienyl, rhodium methylcyclopentadienyl,rhodium ethylcyclopentadienyl, rhodium pentamethylcyclopentadienyl,rhodium 2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphine, rhodium5,10,15,20-tetraphenyl-21H,23H-porphine, rhodiumbis(5-[[4-(dimethylamino)phenyl]imino]-8(5H)-quinolinone), rhodium2,11,20,29-tetra-tert-butyl-2,3-naphthalocyanine, rhodium2,9,16,23-tetraphenoxy-29H,31H-phthalocyanine, rhodium5,10,15,20-tetrakis(pentafluorophenyl)-21H,23H-porphine and the1,4-bis(diphenylphosphine)butane, 1,3-bis(diphenylphosphino)propane,2-(2′-di-tert-butylphosphine)biphenyl, acetonitrile, benzonitrile,ethylenediamine, chloroform, 1,2-bis(phenylsulfinyl)ethane,1,3-bis(2,6-diisopropylphenyl)imidazolidene)(3-chloropyridyl),2′-(dimethylamino)-2-biphenylyl, dinorbornylphosphine,2-(dimethylaminomethyl)ferrocene, allyl, bis(diphenylphosphino)butane,(N-succinimidyl)bis(triphenylphosphine), dimethylphenylphosphine,methyldiphenylphosphine, 1,10-phenanthroline, 1,5-cyclooctadiene,N,N,N′,N′-tetramethylethylenediamine, triphenylphosphine,tri-o-tolylphosphine, tricyclohexylphosphine, tributylphosphine,triethylphosphine, 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl,1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene,1,3-bis(mesityl)imidazol-2-ylidene,1,1′-bis(diphenylphosphino)ferrocene, 1,2-bis(diphenylphosphino)ethane,N-methylimidazole, 2,2′-bipyridine, (bicyclo[2.2.1]hepta-2,5-diene),bis(di-tert-butyl(4-dimethylaminophenyl)phosphine), bis(tert-butylisocyanide), 2-methoxyethyl ether, ethylene glycol dimethyl ether,1,2-dimethoxyethane, bis(1,3-diamino-2-propanol),bis(N,N-diethylethylenediamine), 1,2-diaminocyclohexane, pyridine,2,2′:6′,2″-terpyridine, diethyl sulfide, ethylene and amine complexesthereof;potassium hexachloropalladate(IV), sodium hexachloropalladate(IV),ammonium hexachloropaliadate(IV), potassium tetrachloropalladate(II),sodium tetrachloropalladate(II), ammonium tetrachloropalladate(II),bromo(tri-tert-butylphosphine)palladium(I) dimer,(2-methylallyl)palladium(II) chloride dimer,bis(dibenzylideneacetone)palladium(0),tris(dibenzylideneacetone)dipalladium(0),tetrakis(triphenylphosphine)palladium(0),tetrakis(tricyclohexylphosphine)-palladium(0),bis[1,2-bis(diphenylphosphine)ethane]palladium(0),bis(3,5,3′,5′-dimethoxydibenzylideneacetone)palladium(0),bis(tri-tert-butylphosphine)palladium(0),meso-tetraphenyltetrabenzoporphinepalladium,tetrakis(methyldiphenylphosphine)palladium(0),tris(3,3′,3″-phosphinidyne-tris(benzenesulfonato)palladium(0) nonasodiumsalt,1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene(1,4-naphthoquinone)palladium(0),1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene(1,4-naphthoquinone)palladium(0)and the chloroform complex thereof;allylnickel(II) chloride dimer, ammoniumnickel(II) sulfate,bis(1,5-cycloocta-diene)nickel(0),bis(triphenylphosphine)dicarbonylnickel(0),tetrakis(triphenyl-phosphine)nickel(0), tetrakis(triphenylphosphite)nickel(0), potassium hexafluoronickelate(IV), potassiumtetracyanonickelate(II), potassium nickel(IV) paraperiodate, dilithiumtetrabromonickelate(II), potassium tetracyanonickelate(II);platinum(IV) chloride, platinum(IV) oxide, platinum(IV) sulfide,potassium hexachloroplatinate(IV), sodium hexachloroplatinate(IV),ammonium hexachloroplatinate(IV), potassium tetrachloroplatinate(II),ammonium tetrachloroplatinate(II), potassium tetracyanoplatinate(II),trimethyl(methylcyclopentadienyl)platinum(IV),cis-diammintetrachloroplatinum(IV), potassiumtrichloro(ethylene)platinate(II), sodium hexahydroxyplatinate(IV),tetraamineplatinum(II) tetrachloroplatinate(II), tetrabutylammoniumhexachloroplatinate(IV), ethylenebis(triphenylphosphine)platinum(0),platinum(0) 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, platinum(0)2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane,tetrakis(triphenylphosphine)platinum(0), platinum octaethylporphyrine,chloroplatinic acid, carboplatin; chlorobis(ethylene)rhodium dimer,hexarhodium hexadecacarbonyl, chloro(1,5-cyclooctadiene)rhodium dirner,chloro(norbornadiene)rhodium dimer, chloro(1,5-hexadiene)rhodium dimer.

The ligands preferably comprise phosphines of the formula (VII)

PR⁹ ₃  (VII)

where the R⁹ radicals are each independently hydrogen, straight-chain,branched or cyclic C₁-C₂₀-alkyl, C₁-C₂₀-alkylaryl, C₂-C₂₀-alkenyl,C₂-C₂₉-alkynyl, C₁-C₂₀-carboxylate, C₁-C₂₀-alkoxy, C₁-C₂₀-alkenyloxy,C₁-C₂₀-alkynyloxy, C₂-C₂₀-alkoxycarbonyl, C₁-C₂₀-alkylthio,C₁-C₂₀-alkylsulfonyl, C₁-C₂₀-alkylsulfinyl, silyl and/or theirderivatives and/or phenyl substituted by at least one R¹⁰, or naphthylsubstituted by at least one R¹⁰. R¹⁰ in each occurrence is independentlyhydrogen, fluorine, chlorine, bromine, iodine, NH₂, nitro, hydroxyl,cyano, formyl, straight-chain, branched or cyclic C₁-C₂₀-alkyl,C₁-C₂₀-alkoxy, HN(C₁-C₂₀-alkyl), N(C₁-C₂₀-alkyl)₂, —CO₂—(C₁-C₂₀-alkyl),—CON(C₁-C₂₀-alkyl)₂, —OCO(C₁-C₂₀-alkyl), NHCO(C₁-C₂₀-alkyl), —SO₃M,—SO₂N(R¹¹)M, —CO₂M, —PO₃M₂, —AsO₃M₂, —SiO₂M, —C(CF₃)₂OM (M=H, Li, Na orK), where R¹¹ is hydrogen, fluorine, chlorine, bromine, iodine,straight-chain, branched or cyclic C₁-C₂₀-alkyl, C₂-C₂₀-alkenyl,C₂-C₂₀-alkynyl, C₁-C₂₀-carboxylate, C₁-C₂₀-alkoxy, C₁-C₂₀-alkenyloxy,C₁-C₂₀-alkynyloxy, C₂-C₂₀-alkoxycarbonyl, C₁-C₂₀-alkylthio,C₁-C₂₀-alkylsulfonyl, silyl and/or their derivatives, aryl,C₁-C₂₀-arylalkyl, C₁-C₂₀-alkylaryl, phenyl and/or biphenyl. Preferably,the R⁹ groups are all identical.

Suitable phosphines(VII) are for example trimethylphosphine,triethylphosphine, tripropylphosphine, thisopropylphosphine,tributylphosphine, triisobutylphosphine, triisopentylphosphine,trihexylphosphine, tricyclohexylphosphine, trioctylphosphine,tridecylphosphine, triphenylphosphine, diphenylmethylphosphine,phenyldimethylphosphine, tri(o-tolyl)phosphine, tri(p-tolyl)phosphine,ethyldiphenylphosphine, dicyclohexylphenylphosphine,2-pyridyl-diphenylphosphine, bis(6-methyl-2-pyridyl)phenylphosphine,tri(p-chlorophenyl)-phosphine, tri(p-methoxyphenyl)phosphine,diphenyl(2-sulfonatophenyl)-phosphine; potassium, sodium and ammoniumsalts of diphenyl(3-sulfonatophenyl)phosphine,bis(4,6-dimethyl-3-sulfonatophenyl)(2,4-dimethylphenyl)phosphine,bis(3-sulfonatophenyl)phenylphosphines, t4,6-dimethyl-3-sulfonatophenyl)phosphines,tris(2-sulfonatophenyl)phosphines, tris(3-sulfonatophenyl)phosphines,2-bis(diphenylphosphinoethyl)trimethylammonium iodide,2′-dicyclohexylphosphino-2,6-dimethoxy-3-sulfonato-1,1′-biphenyl sodiumsalt, trimethyl phosphite and/or triphenyl phosphite.

The ligands more preferably comprise bidentate ligands of the generalformula

R⁹M″-Z-M″R⁹  (VIII).

In this formula, each M″ independently is N, P, As or Sb.

M″ is preferably the same in the two occurrences and more preferably isa phosphorus atom.

Each R⁹ group independently represents the radicals described underformula (VIII). The R⁹ groups are preferably all identical.

Z is preferably a bivalent bridging group which contains at least 1bridging atom, preferably from 2 to 6 bridging atoms.

Bridging atoms can be selected from carbon, nitrogen, oxygen, siliconand sulfur atoms. Z is preferably an organic bridging group containingat least one carbon atom. Z is preferably an organic bridging groupcontaining 1 to 6 bridging atoms, of which at least two are carbonatoms, which may be substituted or unsubstituted.

Preferred Z groups are —CH₂—, —CH₂—CH₂—, —CH₂—CH₂—CH₂—,—CH₂—CH(CH₃)—CH₂—, —CH₂—C(CH₃)₂—CH₂—, —CH₂—C(C₂H₅)—CH₂—,—CH₂—Si(CH₃)₂—CH₂—, —CH₂—O—CH₂—, —CH₂—CH₂—CH₂—CH₂—, —CH₂—CH(C₂H₅)—CH₂—,—CH₂—CH(n-Pr)—CH and —CH₂—CH(n-Bu)—CH₂—, substituted or unsubstituted1,2-phenyl, 1,1′-cyclohexyl, 1,1′- or 1,2-ferrocenyl radicals,2,2′-(1,1′-biphenyl), 4,5-xanthene and/or oxydi-2,1-phenylene radicals.

Examples of suitable bidentate phosphine ligands (VIII) are for example1,2-bis(dimethylphosphino)ethane, 1,2-bis(diethylphosphino)ethane,1,2-bis(dipropylphosphino)ethane, 1,2-bis(diisopropylphosphino)ethane,1,2-bis(dibutylphosphino)ethane, 1,2-bis(di-tert-butylphosphino)ethane,1,2-bis(dicyclohexylphosphino)ethane, 1,2-bis(diphenylphosphino)ethane;1,3-bis(dicyclohexylphosphino)propane,1,3-bis(diisopropylphosphino)propane,1,3-bis(di-tert-butylphosphino)propane,1,3-bis(diphenylphosphino)propane; 1,4-bis(diisopropylphosphino)butane,1,4-bis(diphenylphosphino)butane; 1,5-bis(dicyclohexylphosphino)pentane;1,2-bis(di-tert-butylphosphino)benzene,1,2-bis(diphenylphosphino)benzene,1,2-bis(dicyclohexylphosphino)benzene,1,2-bis(dicyclopentylphosphino)benzene,1,3-bis(di-tert-butylphosphino)benzene,1,3-bis(diphenylphosphino)benzene,1,3-bis(dicyclohexylphosphino)benzene,1,3-bis(dicyclopentylphosphino)benzene;9,9-dimethyl-4,5-bis(diphenylphosphino)-xanthene,9,9-dimethyl-4,5-bis(diphenylphosphino)-2,7-di-tert-butylxanthene,9,9-dimethyl-4,5-bis(di-tert-butylphosphino)xanthene,1,1′-bis(diphenylphosphino)-ferrocene,2,2′-bis(diphenylphosphino)-1,1′-binaphthyl,2,2′-bis(di-p-tolylphosphino)-1,1′-binaphthyl,(oxydi-2,1-phenylene)bis(diphenylphosphine),2,5-(diisopropylphospholano)benzene,2,3-O-isopropropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane,2,2′-bis(di-tert-butylphosphino)-1,1′-biphenyl,2,2′-bis(dicyclohexylphosphino)-1,1′-biphenyl,2,2′-bis(diphenylphosphino)-1,1′-biphenyl,2-(di-tert-butylphosphino)-2′-(N,N-dimethylamino)biphenyl,2-(dicyclohexylphosphino)-2′-(N,N-dimethylamino)biphenyl,2-(diphenylphos-phino)-2′-(N,N-dimethylamino)biphenyl,2-(diphenylphosphino)ethylamine, 2-[2-(diphenylphosphino)ethyl]pyridine;potassium, sodium and ammonium salts of1,2-bis(di-4-sulfonatophenylphosphino)benzene,(2,2′-bis[[bis(3-sulfonato-phenyl)phosphino]methyl]-4,4′,7,7′-tetrasulfonato-1,1′-binapthyl,(2,2°-bis[[bis(3-sulfonatophenyl)phosphino]methyl]-5,5′-tetrasulfonato-1,1-biphenyl,(2,2′-bis[[bis(3-sulfonatophenyl)phosphino]methyl]-1,1¹-binapthyl,(2,2′-bis[[bis(3-sulfonatophenyl)phosphino]methyl]-1,1′-biphenyl,9,9-dimethyl-4,5-bis(diphenylphosphino)-2,7-sulfonatoxanthene,9,9-dimethyl-4,5-bis(di-tert-butylphosphino)-2,7-sulfonatoxanthene,1,2-bis(di-4-sulfonatophenylphosphino)-benzene,meso-tetrakis(4-sulfonatophenyl)porphine,meso-tetrakis(2,6-dichloro-3-sulfonatophenyl)porphine,meso-tetrakis(3-sulfonatomesityl)porphine,tetrakis(4-carboxyphenyl)porphine and5,11,17,23-sulfonato-25,26,27,28-tetrahydroxycalix[4]arene.

Moreover, the ligands of the formula (VII) and (VIII) can be attached toa suitable polymer or inorganic substrate by the R⁹ radicals and/or thebridging group.

The molar transition metal/ligand ratio of the catalyst system is in therange 1:0.01 to 1:100, preferably in the range from 1:0.05 to 1:10 andmore preferably in the range from 1:1 to 1:4.

The reactions in the process stages a), b), c) and d) preferably takeplace, if desired, in an atmosphere comprising further gaseousconstituents such as nitrogen, oxygen, argon, carbon dioxide forexample; the temperature is in the range from −20 to 340° C., moreparticularly in the range from 20 to 180° C., and total pressure is inthe range from 1 to 100 bar.

The products and/or the transition metal and/or the transition metalcompound and/or catalyst system and/or the ligand and/or startingmaterials are optionally isolated after the process stages a), b), c),and d) by distillation or rectification, by crystallization orprecipitation, by filtration or centrifugation, by adsorption orchromatography or other known methods.

According to the present invention, solvents, auxiliaries and any othervolatile constituents are removed by distillation, filtration and/orextraction for example.

The reactions in the process stages a), b), c), and d) are preferablycarried out, if desired, in absorption columns, spray towers, bubblecolumns, stirred tanks, trickle bed reactors, flow tubes, loop reactorsand/or kneaders.

Suitable mixing elements include for example anchor, blade, MIG,propeller, impeller and turbine stirrers, cross beaters, disperserdisks, hollow (sparging) stirrers, rotor-stator mixers, static mixers,Venturi nozzles and/or mammoth pumps.

The intensity of mixing experienced by the reaction solutions/mixturespreferably corresponds to a rotation Reynolds number in the range from 1to 1 000 000 and preferably in the range from 100 to 100 000.

It is preferable for an intensive commixing of the respective reactantsetc. to be effected by an energy input in the range from 0.080 to 10kW/m³, preferably 0.30-1.65 kW/m³.

During the reaction, the particular catalyst A or C is preferablyhomogeneous and/or heterogeneous in action. Therefore, the particularheterogeneous catalyst is effective during the reaction as a suspensionor bound to a solid phase.

Preferably, the catalyst A is generated in situ before the reactionand/or at the start of the reaction and/or during the reaction.

Preferably, the particular reaction takes place in a solvent as asingle-phase system in homogeneous or heterogeneous mixture and/or inthe gas phase.

When a multi-phase system is used, a phase transfer catalyst may be usedin addition.

The reactions of the present invention can be carried out in liquidphase, in the gas phase or else in supercritical phase. The particularcatalyst A or C is preferably used in the case of liquids in homogeneousform or as a suspension, while a fixed bed arrangement is advantageousin the case of gas phase or supercritical operation.

Suitable solvents are water, alcohols, e.g. methanol, ethanol,isopropanol, n-propanol, n-butanol, isobutanol, tert-butanol, n-amylalcohol, isoamyl alcohol, tert-amyl alcohol, n-hexanol, n-octanol,isooctanol, n-tridecanol, benzyl alcohol, etc. Preference is furthergiven to glycols, e.g. ethylene glycol, 1,2-propanediol,1,3-propanediol, 1,3-butanedial, 1,4-butanediol, diethylene glycol etc.;aliphatic hydrocarbons, such as pentane, hexane, heptane, octane, andpetroleum ether, naphtha, kerosene, petroleum, paraffin oil, etc.;aromatic hydrocarbons, such as benzene, toluene, xylene, mesitylene,ethylbenzene, diethylbenzene, etc.; halogenated hydrocarbons, such asmethylene chloride, chloroform, 1,2-dichloroethane, chlorobenzene,carbon tetrachloride, tetrabromoethylene, etc.; alicyclic hydrocarbons,such as cyclopentane, cyclohexane, and methylcyclohexane, etc.; ethers,such as anisole (methyl phenyl ether), tert-butyl methyl ether, dibenzylether, diethyl ether, dioxane, diphenyl ether, methyl vinyl ether,tetrahydrofuran, triisopropyl ether etc.; glycol ethers, such asdiethylene glycol diethyl ether, diethylene glycol dimethyl ether(diglyme), diethylene glycol monobutyl ether, diethylene glycolmonomethyl ether, 1,2-dimethoxyethane (DME, monoglyme), ethylene glycolmonobutyl ether, triethylene glycol dimethyl ether (triglyme),triethylene glycol monomethyl ether etc.; ketones, such as acetone,diisobutyl ketone, methyl n-propyl ketone; methyl ethyl ketone, methylisobutyl ketone etc.; esters, such as methyl formate, methyl acetate,ethyl acetate, n-propyl acetate, and n-butyl acetate, etc.; carboxylicacids, such as formic acid, acetic acid, propionic acid, butyric acid,etc. One or more of these compounds can be used, alone or incombination.

Suitable solvents also encompass the phosphinic acid sources and olefinsused. These have advantages in the form of higher space-time yield.

It is preferable that the reaction be carried out under the autogenousvapor pressure of the olefin and/or of the solvent.

Preferably, R¹, R², R³ and R⁴ of olefin (IV) are the same or differentand each is independently H, methyl, ethyl, n-propyl, isopropyl,n-butyl, isobutyl, tert-butyl and/or phenyl.

Preference is also given to using functionalized olefins such as allylisothiocyanate, allyl methacrylate, 2-allylphenol, N-allylthiourea,thiazoline, allyltrimethylsillane, allyl acetate, allyl acetoacetate,allyl alcohol, allylamine, allylbenzene, allyl cyanide, allylcyanoacetate, allylanisole, trans-2-pentenal, cis-2-pentenenitrile,1-penten-3-ol, 4-penten-1-ol, 4-penten-2-ol, trans-2-hexenal,trans-2-hexen-1-ol, cis-3-hexen-1-ol, 5-hexen-1-ol, styrene,-methylstyrene, 4-methylstyrene, vinyl acetate, 9-vinylanthracene,2-vinylpyridine, 4-vinylpyridine and 1-vinyl-2-pyrrolidone.

The partial pressure of the olefin during the reaction is preferably0.01-100 bar and more preferably 0.1-10 bar.

The phosphinic acid/olefin molar ratio for the reaction is preferably inthe range from 1:10 000 to 1:0.001 and more preferably in the range from1:30 to 1:0.01.

The phosphinic acid/catalyst molar ratio for the reaction is preferablyin the range from 1:1 to 1:0.00000001 and more preferably in the rangefrom 1:0.01 to 1:0.000001.

The phosphinic acid/solvent molar ratio for the reaction is preferablyin the range from 1:10 000 to 1:0 and more preferably in the range from1:50 to 1:1.

One method the present invention provides for producing compounds of theformula (II) comprises reacting a phosphinic acid source with olefins inthe presence of a catalyst and freeing the product (II)(alkylphosphonous acid, salts or esters) of catalyst, transition metalor transition metal compound as the case may be, ligand, complexingagent, salts and by-products.

The present invention provides that the catalyst, the catalyst system,the transition metal and/or the transition metal compound are separatedoff by adding an auxiliary 1 and removing the catalyst, the catalystsystem, the transition metal and/or the transition metal compound byextraction and/or filtration.

The present invention provides that the ligand and/or complexing agentis separated off by extraction with auxiliary 2 and/or distillation withauxiliary 2.

Auxiliary 1 is preferably water and/or at least one member of the groupof metal scavengers. Preferred metal scavengers are metal oxides, suchas aluminum oxide, silicon dioxide, titanium dioxide, zirconium dioxide,zinc oxide, nickel oxide, vanadium oxide, chromium oxide, magnesiumoxide, Celite®, kieselguhr; metal carbonates, such as barium carbonate,calcium carbonate, strontium carbonate; metal sulfates, such as bariumsulfate, calcium sulfate, strontium sulfate; metal phosphates, such asaluminum phosphate, vanadium phosphate, metal carbides, such as siliconecarbide; metal aluminates, such as calcium aluminate; metal silicates,such as aluminum silicate, chalks, zeolites, bentonite, montmorillonite,hectorite; functionalized silicates, functionalized silica gels, such asSiliaBond®, QuadraSil™ functionalized polysiloxanes, such as Deloxan®;metal nitrides, carbon, activated carbon, mullite, bauxite, antimonite,scheelite, perovskite, hydrotalcite, functionalized and unfunctionalizedcellulose, chitosan, keratin, heteropolyanions, ion exchangers, such asAmberlite™, Amberjet™, Ambersep™, Dowex®, Lewatit®, ScavNet®;functionalized polymers, such as Chelex®, QuadraPure™, Smopex®,PolyOrgs®; polymer-bound phosphanes, phosphane oxides, phosphinates,phosphonates, phosphates, amines, ammonium salts, amides, thioamides,urea, thioureas, triazines, imidazoles, pyrazoles, pyridines,pyrimidines, pyrazines, thiols, thiol ethers, thiol esters, alcohols,alkoxides, ethers, esters, carboxylic acids, acetates, acetals,peptides, hetarenes, polyethyleneimine/silicon dioxide, and/ordendrimers.

It is preferable that the amounts added of auxiliary 1 correspond to0.1-40% by weight loading of the metal on auxiliary 1.

It is preferable that auxiliary 1 be used at temperatures of from 20 to90° C.

It is preferable that the residence time of auxiliary 1 be from 0.5 to360 minutes.

Auxiliary 2 is preferably the aforementioned solvent of the presentinvention as are preferably used in process stage a).

The esterification of the monocarboxy-functionalized dialkylphosphinicacid (III) or of the monofunctionalized dialkylphosphinic acid (VI)and/or (VI′) or of the alkylphosphonous acid derivatives (II) and alsoof the phosphinic acid source (I) to form the corresponding esters canbe achieved for example by reaction with higher-boiling alcohols byremoving the resultant water by azeotropic distillation, or by reactionwith epoxides (alkylene oxides).

Preferably, following step a), the alkylphosphonous acid (II) isdirectly esterified with an alcohol of the general formula M-OH and/orM′-OH or by reaction with alkylene oxides, as indicated hereinbelow.

M-OH preferably comprises primary, secondary or tertiary alcohols havinga carbon chain length of C₁-C₁₈. Particular preference is given tomethanol, ethanol, propanol, isopropanol, n-butanol, 2-butanol,tert-butanol, amyl alcohol and/or hexanol.

M′-OH preferably comprises ethylene glycol, 1,2-propylene glycol,1,3-propylene glycol, 1,4-butanediol, 2,2-dimethylpropane-1,3-diol,neopentyl glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, glycerol,trishydroxymethylethane, trishydroxymethylpropane, pentaerythritol,sorbitol, mannitol, α-naphthol, polyethylene glycols, polypropyleneglycols and/or EO-PO block polymers.

Also useful as M-OH and M′-OH are mono- or polyhydric unsaturatedalcohols having a carbon chain length of C₁-C₁₈, for examplen-but-2-en-1-ol, 1,4-butenediol and allyl alcohol.

Also useful as M-OH and M′-OH are reaction products of monohydricalcohols with one or more molecules of alkylene oxides, preferably withethylene oxide and/or 1,2-propylene oxide. Preference is given to2-methoxyethanol, 2-ethoxyethanol, 2-n-butoxyethanol,2-(2′-ethylhexyloxy)ethanol, 2-n-dodecoxyethanol, methyl diglycol, ethyldiglycol, isopropyl diglycol, fatty alcohol polyglycol ethers and arylpolyglycol ethers.

M-OH and M′-OH are also preferably reaction products of polyhydricalcohols with one or more molecules of alkylene oxide, more particularlydiglycol and triglycol and also adducts of 1 to 6 molecules of ethyleneoxide or propylene oxide onto glycerol, trishydroxymethylpropane orpentaerythritol.

Useful M-OH and M′-OH further include reaction products of water withone or more molecules of alkylene oxide. Preference is given topolyethylene glycols and poly-1,2-propylene glycols of various molecularsizes having an average molecular weight of 100-1000 g/mol and morepreferably of 150-350 g/mol.

Preference for use as M-OH and M′-OH is also given to reaction productsof ethylene oxide with poly-1,2-propylene glycols or fatty alcoholpropylene glycols; similarly reaction products of 1,2-propylene oxidewith polyethylene glycols or fatty alcohol ethoxylates. Preference isgiven to such reaction products with an average molecular weight of100-1000 g/mol, more preferably of 150-450 g/mol.

Also useful as M-OH and M′-OH are reaction products of alkylene oxideswith ammonia, primary or secondary amines, hydrogen sulfide, mercaptans,oxygen acids of phosphorus and C₂-C₆ dicarboxylic acids. Suitablereaction products of ethylene oxide with nitrogen compounds aretriethanolamine, methyldiethanolamine, n-butyldiethanolamine,n-dodecyldiethanolamine, dimethylethanolamine,n-butylmethylethanolamine, di-n-butylethanolamine,n-dodecylmethylethanolamine, tetrahydroxyethylethylenediamine orpentahydroxyethyldiethylenetriamine.

Preferred alkylene oxides are ethylene oxide, 1,2-propylene oxide,12-epoxybutane, 1,2-epoxyethylbenzene, (2,3-epoxypropyl)benzene,2,3-epoxy-1-propanol and 3,4-epoxy-1-butene.

Suitable solvents are the solvents mentioned in process step a) and alsothe M-OH and M′-OH alcohols used and the alkylene oxides. These offeradvantages in the form of a higher space-time yield.

The reaction is preferably carried out under the autogenous vaporpressure of the employed alcohol M-OH, M′-OH and alkylene oxide and/orof the solvent.

Preferably, the reaction is carried out at a partial pressure of theemployed alcohol M-H, M′-OH and alkylene oxide of 0.1-100 bar, morepreferably at a partial pressure of the alcohol of 0-10 bar.

The reaction is preferably carried out at a temperature in the rangefrom −20 to 340° C. and is more preferably carried out at a temperaturein the range from 20 to 180° C.

The reaction is preferably carried out at a 0 al pressure in the rangefrom 1 to 100 bar.

The reaction is preferably carried out in a molar ratio for the alcoholor alkylene oxide component to the phosphinic acid source (I) oralkylphosphonous acid (II) or monofunctionalized dialkylphosphinic acid(VI) and/or (VI′) or monocarboxy-functionalized dialkylphosphinic acid(III) ranging from 10 000:1 to 0.01:1 and more preferably from 1000:1 to0.1:1.

The reaction is preferably carried out in a molar ratio for thephosphinic acid source (I) or alkylphosphonous acid (II) ormonofunctionalized dialkylphosphinic acid (VI) or monofunctionalizeddialkylphosphinic acid (VII) or monocarboxy-functionalizeddialkylphosphinic acid (III) to the solvent ranging from 1:10 000 to 1:0and more preferably in a phosphinic acid/solvent molar ratio rangingfrom 1:50 to 1:1,

Particularly preferred catalysts B as used in process stage b) areperoxo compounds such as peroxomonosulfuric acid, potassiummonopersulfate (potassium peroxomonosulfate), Caroat™, Oxone™,peroxodisulfuric acid, potassium persulfate (potassium peroxodisulfate),sodium persulfate (sodium peroxodisulfate), ammonium persulfate(ammonium peroxodisulfate).

Particularly preferred catalysts B are compounds capable of formingperoxides in the solvent system, such as sodium peroxide, sodiumperoxide hydrates, sodium peroxide diperoxohydrate, sodium peroxidediperoxohydrates, lithium peroxide, lithium peroxide hydrates, calciumperoxide, strontium peroxide, barium peroxide, magnesium peroxide, zincperoxide, potassium hyperoxide, potassium hyperoxide hydrates, sodiumperoxoborate, sodium peroxoborate hydrates, potassium peroxoborateperoxohydrate, magnesium peroxoborate, calcium peroxoborate, bariumperoxoborate, strontium peroxoborate, potassium peroxoborate,peroxomonophosphoric acid, peroxodiphosphoric acid, potassiumperoxodiphosphate, ammonium peroxodiphosphate, potassium ammoniumperoxodiphosphates, sodium carbonate peroxohydrate, urea peroxohydrate,ammonium oxalate peroxide, barium peroxide peroxohydrate, bariumperoxide peroxohydrate, calcium hydrogen peroxides, calcium peroxideperoxohydrate, ammonium triphosphate diperoxophosphate hydrate,potassium fluoride peroxohydrate, potassium fluoride triperoxohydrate,potassium fluoride diperoxohydrate, sodium pyrophosphatediperoxohydrate, sodium pyrophosphate diperoxohydrate octahydrate,potassium acetate peroxohydrate, sodium phosphate peroxohydrate, sodiumsilicate peroxohydrate.

Preferred catalysts B are hydrogen peroxide, performic acid, peraceticacid, benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide,2,4-dichlorobenzoyl peroxide, decanoyl peroxide, lauryl peroxide, cumenehydroperoxide, pinene hydroperoxide, p-menthane hydroperoxide, t-butylhydroperoxide, acetylacetone peroxide, methyl ethyl ketone peroxide,succinic acid peroxide, dicetyl peroxydicarbonate, t-butylperoxyacetate, t-butylperoxymaleic acid, t-butyl peroxybenzoate, acetylcyclohexylsulfonyl peroxide,

Preferred catalysts B are water-soluble azo compounds. Particularpreference is given to azo initiators such as VAZO® 522,2′-azobis(2,4-dimethylvaleronitrile), VAZO® 64(azobis(isobutyronitrile), AIBN), VAZO® 672,2′-azobis(2-methyl-butyronitrile), VAZO® 881,1′-azobis(cyclohexane-1-carbonitrile), VAZO® 68 fromDupont-Biesteritz, V-702,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), V-652,2′-azobis(2,4-dimethylvaleronitrile), V-601 dimethyl2,2′-azobis(2-methylpropionate), V-592,2′-azobis(2-methylbutyronitrile), V-401,1′-azobis(cyclohexane-1-carbonitrile), VF-0962,2′-azobis[N-(2-propenyl)-2-methylpropionamide], V-301-[(cyano-1-methylethyl)azo]formamide, VAm-1102,2′-azobis(N-butyl-2-methyl-propionamide), VAm-1112,2′-azobis(N-cyclohexyl-2-methylpropionamide), VA-046B2,2′-azobis[2-(2-imidazolin-2-yl)propane disulfate dihydrate, VA-0572,2′-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]tetrahydrate,VA-061 2,2′-azobis[2-(2-imidazolin-2-yl)propane], VA-0802,2′-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide},VA-085 2,2′-azobis{2-methyl-N-[2-(1-hydroxybutyl)]propionamide}, VA-0862,2′-azobis[2-methyl-N-(2-hydroxy-ethyl)propionamide] from WakoChemicals.

It is also possible to use azo initiators such as2-tert-butylazo-2-cyanopropane, dimethyl azodiisobutyrate,azodiisobutyronitrile, 2-tert-butylazo-1-cyano-cyclohexane,1-tert-amylazo-1-cyanocyclohexane. Preference is further given to alkylperketals such as 2,2-bis-(tert-butylperoxy)butane, ethyl3,3-bis(tert-butylperoxy)butyrate, 1,1-di(tert-butylperoxy)cyclohexane,

Preferred catalysts B are also metals, metal hydrides and metalalkoxides such as, for example, lithium, lithium hydride, lithiumaluminohydride, methyllithium, butyllithium, tert-butyllithium, lithiumdiisopropylamide, sodium, sodium hydride, sodium borohydride, sodiummethoxide, sodium ethoxide, sodium butoxide, potassium methoxide,potassium ethoxide or potassium butoxide.

Preferably the catalyst B is used in amounts of 0.05 to 5 mol % based onthe respective allyl alcohols (V) and/or acroleins (V′).

Preferably, the catalyst B is used in amounts of 0.001 to 10 mol %,based on the phosphorus-containing compound.

The catalyst B is preferably metered in at a rate of 0.01 to 10 mol % ofcatalyst per hour, based on the phosphorus-containing compound.

Suitable solvents are those used above in process stage a).

The initiator B is preferably metered in at a rate of 0.01 to 10 mol %of catalyst per hour, based on the phosphorus-containing compound.

The reaction of the alkylphosphonous acids (II) with an allyl alcohol(V) and/or acrolein (V′) is preferably carried out at a temperature of 0to 250° C., more preferably at 20 to 200° C. and more particularly at 50to 150° C.

The atmosphere for the reaction with an allyl alcohol (V) and/oracrolein (V′) preferably consists of constituents of the solvent and theallyl alcohol (V) and/or acrolein (V′) to an extent of 50% to 99.9% byweight, preferably 70-95% by weight.

The reaction during the addition of allyl alcohol (V) and/or acrolein(V′) is preferably carried out with a pressure of 1-20 bar.

In a further embodiment of the method, the product mixture obtainedafter process stage a) and/or b) is worked up.

In a further embodiment of the method, the product mixture obtainedafter process stage a) is worked up and thereafter themonofunctionalized dialkylphosphonic acids and/or their esters andalkali metal salts obtained after process stage b) are reacted inprocess stage c).

The invention further provides a method in step b) for continuousproduction of monofunctionalized dialkylphosphinic esters (VI) byreaction of alkylphosphonic esters (II) with an acrolein (VI′) in thepresence of metal alkoxides (catalyst B), which method comprises

a) initially charging a self-contained reactor configured to circulatethe reaction mixture and equipped with cooling means and also anoverflow with a volume corresponding to the reactor volume of themonofunctionalized dialkylphosphinic esters (VI) to be produced,optionally mixed with the alcohol corresponding to the metal alkoxide assolvent, and recirculating,b) the alkylphosphonous ester (II), the acrolein (VI′) and also analcoholic solution of the metal alkoxide being continuously introducedinto the reactor with cooling of the recirculated reactor contents, andreacted at a temperature of about 0 to 80° C. in the course of about5-120 minutes, wherein the molar ratio of the alkylphosphonous ester(II) to the acrolein (VI′) is about 1:0.9-2 and the amount of the metalalkoxide, based on the alkylphosphonous ester (II), is about 0.1 to 5mol %; andc) continuously withdrawing, over the overflow of the reactor, a mixturecomprising the process product and separating the monofunctionalizeddialkyl-phosphinic ester (VI) from the mixture by distillation.

In a preferred embodiment of the method according to the presentinvention, the reaction of the reaction components is carried out at atemperature of 20 to 50° C. The charging of the reactor with thereaction components and the catalyst solution can be carried out forexample by

a) passing the alkylphosphonous ester (II), the acrolein (V′) and alsothe alcoholic solution of the metal alkoxide into the reactorseparately,b) passing a mixture of the alkylphosphonous ester (II) with theacrolein (V′) into the reactor separately from the alcoholic solution ofthe metal alkoxide, orc) passing a mixture of the alkylphosphonous ester (II) with thealcoholic solution of the metal alkoxide into the reactor separatelyfrom the acrolein (V′),

It is further advantageous when the alcohol used as solvent and/or thealcoholic component of the metal alkoxide correspond to the alcoholiccomponent of the alkylphosphonous ester (II).

When alkylphosphonous ester (II) and the alcoholic metal alkoxidesolution are used with different alcoholic components, a mixed productwill be obtained as process product.

Lastly, preferred features of the invention consist in the molar ratioof alkylphosphonous ester (II) to acrolein (V′) being in the range from1:1-1.3, the amount of catalyst B based on the alkylphosphonous ester(II) being 1-5 mol % and the amount of alcohol used as solvent being0.1-1000 mol per mole of alkylphosphonous ester.

The method of the present invention makes it possible to producemonofunctionaiized dialkylphosphinic ester (VI') continuously on anindustrial scale in a hitherto unattained yield of about 90% of theory.

The conversion described in step c) to the mono-carboxyfunctionalizeddialkylphosphinic acid, its salts and esters is achieved throughselective oxidation of the monofunctionalized dialkylphosphinic acid,its salts or esters (VI) and/or (VI') by means of an oxidizing agent, anoxidizing agent and water or by means of oxygen and water in thepresence of a catalyst C.

Preferred oxidizing agents and/or oxygen formers are potassiumpermanganate, manganese dioxide, chromium trioxide, potassiumdichromate, pyridine dichromate, pyridine chlorochromate, Collinsreagent, Jones reagent, Corey-Gilman-Ganem reagent, (Dess-Martin)periodinane, o-iodoxybenzoic acid, ruthenium tetroxide, rutheniumdioxide, tetra-n-propyl perruthenate, ruthenium trichloride/sodiumperiodate, ruthenium dioxide/sodium periodate, chlorine, hypochlorite,peracids, for example hydrogen peroxide, performic acid and peraceticacid, nitroxyl free radicals, for example 2,2,6,6-tetramethylpiperidineN-oxide (TEMPO).

In addition to the abovementioned oxidizing agents and/or oxygenformers, all those mentioned as catalyst B in method step b) are alsosuitable.

The reaction is preferably carried out in a dialkylphosphinicacid/oxidizing agent molar ratio of 1:10 to 1:0.1, more preferably in adialkylphosphinic acid/oxidizing agent molar ratio of 1:2 to 1:0.25.

The catalyst C as used for method step c) for the reaction of themonofunctionalized dialkylphosphinic acid derivative (VI) or (VI') withoxygen and water to form the end product, the monocarboxy-functionalizeddialkylphosphinic acid derivative (III), may preferably be the catalystA.

The transition metals for catalyst C preferably additionally compriseelements from the first transition group such as gold for example.

In addition to the sources of transition metals and transition metalcompounds that were listed under catalyst A it is also possible to usethe following transition metals and transition metal compounds:

gold, colloidal gold, ruthenium, ruthenium on charcoal, on carbon, onalumina, platinum-palladium-gold alloy, gold-nickel alloy,gold-germanium alloy, gold-platinum alloy, gold-palladium alloy,gold-beryllium alloy, platinum-ruthenium alloy, palladium-rutheniumalloy, gold(I) and/or gold(III), ruthenium(II) and/or ruthenium(III)and/or ruthenium(IV) chloride, bromide, iodide, oxide, cyanide,potassium cyanide, sodium cyanide, sulfide, sulfate, hydride,nitrosylchloride, nitrosyInitrate, bathophenanthroline disulfonatesodium salt, thiosulfate, perchlorate, cyclopentadienyl,ethylcyclopentadienyl, pentamethylcyclopenta-dienyl, indenyl,2-methylallyl, propionate, acetate, acetylacetonate,hexafluoro-acetylacetonate, tetrafluoroborate, potassium thiocyanate,sodium thiocyanate, trifluoroacetate,bis(trifluoromethanesulfonyl)imidate, hexafluoroantimonate,2-pyridinecarboxylate and their 1,4-bis(diphenylphosphine)butane,1,3-bis(di-phenylphosphino)propane,2-(2′-di-tert-butylphosphine)biphenyl, acetonitrile, benzonitrile,dinorbornylphosphine, 1,4-bis(diphenylphosphino)butane,dimethyl-phenylphosphine, methyldiphenylphosphine, triphenylphosphine,tri-o-tolyl-phosphine, tricyclohexylphosphine, tributylphosphine,tri-tert-butylphosphine, trimethylphosphine, triethylphosphine,2,2′-bis(diphenylphosphino)-1,1′-binaphthyl,1,3-bis(mesityl)imidazol-2-ylidene,1,1′-bis(diphenylphosphino)ferrocene,(1,1′-bi-phenyl-2-yl)di-tert-butylphenyl)phosphite,1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene,2-dicyclohexyl(2′,4′,6′-triisopropylbiphenyl)phosphine, dimethylsulfide, tris(2,4-di-tert-butylphenyl) phosphite,tris(para-trifluoromethylphenyl)phosphine,bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)ethane,N-methyl-imidazole, 1,10-phenanthroline,4,7-diphenyl-1,10-phenanthroline, 1,5-cyclo-octadiene,1,3,5-cyclooctatriene, naphthalene, p-cymene, 3-methyl-2-butenylidene,benzylidene, pyridine, 2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphine,5,10,15,20-tetraphenyl-21H,23H-porphine,N,N,N′,N′-tetramethylethylenediamine, tri-o-tolylphosphine,2,2′-bis(diphenylphosphino)-1,1′-binaphthyl,1,1′-bis(diphenylphosphino)ferrocene, 2,2′-bipyridine,(bicyclo[2.2.1]hepta-2,5-diene),bis(di-tert-butyl(4-dimethylaminophenyl)phosphine),2-(di-tert-butylphosphino)ethylamine, (2-(diphenylphosphino)ethylamine,1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene,1,2-diaminocyclohexane, pyridine, carbonyl, ethylenediamine, aminecomplexes; potassium dicyanoaurate(I), sodium tetrachloroaurate(III),potassium gold(III) chloride, sodium aurothiomalate,tris(triphenylphosphinegold)-oxonium tetrafluoroborate, hydrogentetrabromoaurate(III); ammonium hexachlororuthenate(IV), potassiumaquapentachlororuthenate(III),(1,5-cyclo-octadiene)(1,3,5-cyclooctatriene)ruthenium, trirutheniumdodecacarbonyl, Grubbs catalyst.

The proportion of catalyst C based on the monofunctionalizeddialkylphosphinic acid (VI) and/or (VI′) used is preferably in the rangefrom 0.00001 to 20 mol % and more preferably in the range from 0.0001 to10 mol %.

The reaction is preferably carried out in a phosphinic acid/solventmolar ratio of 1:10 000 to 1:0, more preferably in a phosphinicacid/solvent molar ratio of 1:50 to 1:1.

The oxidation temperature is preferably in the range from 30 to 120° C.and more preferably in the range from 50 to 90° C.

The reaction time is preferably in the range from 0.1 to 20 hours.

The reaction is preferably carried out at a total pressure of 1 to 100bar.

Suitable solvents for process stage c) are those used above in processstage a).

The reaction is preferably carried out at an oxygen partial pressure of0.01-100 bar and preferably at 0.1-10 bar.

The oxidation can be carried out in liquid phase, in the gas phase orelse in supercritical phase. In this case the catalyst is used in thecase of liquids, preferably in homogeneous form or as a suspension,while a fixed bed arrangement is of advantage as in the case of gasphase or supercritical operation.

Preferably, the pH of the reaction solution is maintained in a range ofpH 6 to 12 and more preferably in a range of pH 6 to 9 by addition ofalkali metal and/or alkaline earth metal compounds.

Preferred alkali and/or alkaline earth metals are lithium, sodium,potassium, magnesium, calcium, barium. Sodium, potassium, calcium andbarium are particularly preferred.

Preferred alkali and/or alkaline earth metal compounds are their oxides,hydroxides, carbonates and carboxylates.

Preferred alkali and/or alkaline earth metal compounds are lithium,lithium hydroxide, lithium hydride, sodium, sodium hydroxide, sodiumhydride, potassium hydroxide.

Preferably, the oxygen is used as pure oxygen or an oxygen-containingmixture, for example air or oxygen-enriched air.

Preferably, the oxygen is used in the form of oxygen formers such ashydrogen peroxide for example.

The ratio of oxygen to phosphorus-containing compound (VI) or (VI') ispreferably in the range from 1:1 to 1500:1.

The monocarboxy-functionalized dialkylphosphinic acid or salt (III) canthereafter be converted into further metal salts.

The metal compounds which are used in process stage d) preferablycomprise compounds of the metals Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn,Ce, Bi, Sr, Mn, Li, Na, K, more preferably Mg, Ca, Al, Ti, Zn, Sn, Ce,Fe.

Suitable solvents for process stage d) are those used above in processstage a).

The reaction of process stage d) is preferably carried out in an aqueousmedium.

Process stage d) preferably comprises reacting themonocarboxy-functionalized dialkylphosphinic acids, esters and/or alkalimetal salts (III) obtained after process stage c) with metal compoundsof Mg, Ca, Al, Zn, Ti, Sn, Zr, Ce or Fe to form themonocarboxy-functionalized dialkylphosphinic acid salts (III) of thesemetals.

The reaction is carried out in a molar ratio ofmonocarboxy-functionalized dialkylphosphinic acid, ester or salt (III)to metal in the range from 8:1 to 1:3 (for tetravalent metal ions ormetals having a stable tetravalent oxidation state), from 6:1 to 1:3(for trivalent metal ions or metals having a stable trivalent oxidationstate), from 4:1 to 1:3 (for divalent metal ions or metals having astable divalent oxidation state) and from 3:1 to 1:4 (for monovalentmetal ions or metals having a stable monovalent oxidation state).

Preferably, monocarboxy-functionalized dialkylphosphinic acid, ester orsalt (III) obtained in process stage c) is converted into thecorresponding dialkylphosphinic acid and the latter is reacted inprocess stage d) with metal compounds of Mg, Ca, Al, Zn, Ti, Sn, Zr, Ceor Fe to form the monocarboxy-functionalized dialkylphosphinic acidsalts (III) of these metals.

Preferably, monocarboxy-functionalized dialkylphosphinic acid/ester(III) obtained in process stage c) is converted to a dialkylphosphinicacid alkali metal salt and the latter is reacted in process stage d)with metal compounds of Mg, Ca, Al, Zn, Ti, Sn, Zr, Ce or Fe to form themonocarboxy-functionalized dialkylphosphinic acid salts (III) of thesemetals.

The metal compounds of Mg, Ca, Al, Zn, Ti, Sn, Zr, Ce or Fe for processstage d) preferably comprise metals, metal oxides, hydroxides, oxidehydroxides, borates, carbonates, hydroxocarbonates, hydroxocarbonatehydrates, mixed metal hydroxocarbonates, mixed metal hydroxocarbonatehydrates, phosphates, sulfates, sulfate hydrates, hydroxosulfatehydrates, mixed metal hydroxosulfate hydrates, oxysulfates, acetates,nitrates, fluorides, fluoride hydrates, chlorides, chloride hydrates,oxychlorides, bromides, iodides, iodide hydrates, carboxylic acidderivatives and/or alkoxides.

The metal compounds preferably comprise aluminum chloride, aluminumhydroxide, aluminum nitrate, aluminum sulfate, titanyl sulfate, zincnitrate, zinc oxide, zinc hydroxide and/or zinc sulfate.

Also suitable are aluminum metal, fluoride, hydroxychloride, bromide,iodide, sulfide, selenide; phosphide, hypophosphite, antimonide,nitride; carbide, hexafluorosilicate; hydride, calcium hydride,borohydride; chlorate; sodium aluminum sulfate, aluminum potassiumsulfate, aluminum ammonium sulfate, nitrate, metaphosphate, phosphate,silicate, magnesium silicate, carbonate, hydrotalcite, sodium carbonate,borate, thiocyanate oxide, oxide hydroxide, their corresponding hydratesand/or polyaluminum hydroxy compounds, which preferably have an aluminumcontent of 9 to 40% by weight.

Also suitable are aluminum salts of mono-, di-, oligo-, polycarboxylicacids such as, for example, aluminum diacetate, acetotartrate, formate,lactate, oxalate, tartrate, oleate, palmitate, stearate,trifluoromethanesulfonate, benzoate, salicylate, 8-oxyquinolate.

Likewise suitable are elemental, metallic zinc and also zinc salts suchas for example zinc halides (zinc fluoride, zinc chlorides, zincbromide, zinc iodide).

Also suitable are zinc borate, carbonate, hydroxide carbonate, silicate,hexafluorosilicate, stannate, hydroxide stannate, magnesium aluminumhydroxide carbonate; nitrate, nitrite, phosphate, pyrophosphate;sulfate, phosphide, selenide, telluride and zinc salts of the oxoacidsof the seventh main group (hypohalites, halites, halates, for examplezinc iodate, perhalates, for example zinc perchlorate); zinc salts ofthe pseudohalides (zinc thiocyanate, zinc cyanate, zinc cyanide); zincoxides, peroxides, hydroxides or mixed zinc oxide hydroxides.

Preference is given to zinc salts of the oxoacids of transition metals(for example zinc chromate(VI) hydroxide, chromite, molybdate,permanganate, molybdate).

Also suitable are zinc salts of mono-, di-, oligo-, polycarboxylicacids, for example zinc formate, acetate, trifluoroacetate, propionate,butyrate, valerate, caprylate, oleate, stearate, oxalate, tartrate,citrate, benzoate, salicylate, lactate, acrylate, maleate, succinate,salts of amino acids (glycine), of acidic hydroxyl functions (zincphenoxide etc), zinc p-phenolsulfonate, acetylacetonate, stannate,dimethyldithiocarbamate, trifluoromethanesulfonate.

In the case of titanium compounds, metallic titanium is as istitanium(III) and/or (IV) chloride, nitrate, sulfate, formate, acetate,bromide, fluoride, oxychloride, oxysulfate, oxide, n-propoxide,n-butoxide, isopropoxide, ethoxide, 2-ethylhexyl oxide.

Also suitable is metallic tin and also tin salts (tin(II) and/or (IV)chloride); tin oxides and tin alkoxide such as, for example, tin(IV)tert-butoxide.

Cerium(III) fluoride, chloride and nitrate are also suitable.

In the case of zirconium compounds, metallic zirconium is preferred asare zirconium salts such as zirconium chloride, zirconium sulfate,zirconyl acetate, zirconyl chloride. Zirconium oxides and also zirconium(IV) tert-butoxide are also preferred.

The reaction in process stage d) is preferably carried out at a solidscontent of the monocarboxy-functionalized dialkylphosphinic acid saltsin the range from 0.1% to 70% by weight, preferably 5% to 40% by weight.

The reaction in process stage d) is preferably carried out at atemperature of 20 to 250° C., preferably at a temperature of 80 to 120°C.

The reaction in process stage d) is preferably carried out at a pressurebetween 0.01 and 1000 bar, preferably 0.1 to 100 bar.

The reaction in process stage d) preferably takes place during areaction time in the range from 1*10⁻⁷ to 1000 h.

Preferably, the monocarboxy-functionalized dialkylphosphinic acid salt(III) removed after process stage d) from the reaction mixture byfiltration and/or centrifugation is dried.

Preferably, the product mixture obtained after process stage c) reactedwith the metal compounds without further purification.

Preferred solvents are the solvents mentioned in process step a).

The reaction in process stage d), c) and/or b) is preferably carried outin the solvent system given by stage a).

The reaction in process stage d) is preferred in a modified givensolvent system. Acidic components, solubilizers, foam inhibitors, etcare added for this pupose.

In a further embodiment of the method, the product mixture obtainedafter process stage a), b) and/or c) is worked up.

In a further embodiment of the method, the product mixture obtainedafter process stage c) is worked up and thereafter themonocarboxy-functionalized dialkylphosphinic acids and/or salts oresters (III) obtained after process stage c) are reacted in processstage d) with the metal compounds.

Preferably, the product mixture after process stage c) is worked up byisolating the monocarboxy-functionalized dialkylphosphinic acids and/orsalts or esters (IIi) by removing the solvent system, for example byevaporation.

Preferably, the monocarboxy-functionalized dialkylphosphinic acid salt(III) of the metals Mg, Ca, Al, Zn, Ti, Sn, Zr, Ce or Fe selectively hasa residual moisture content of 0.01% to 10% by weight, preferably of0.1% to 1% by weight, an average particle size of 0.1 to 2000 μm,preferably of 10 to 500 μm, a bulk density of 80 to 800 g/l, preferably200 to 700 g/l, and a Pfrengle flowability of 0.5 to 10, preferably of 1to 5.

The molded articles, films, threads and fibers more preferably containfrom 5% to 30% by weight of the monocarboxy-functionalizeddialkylphosphinic acid/ester/salts produced according to one or more ofclaims 1 to 13, from 5% to 90% by weight of polymer or mixtures thereof,from 5% to 40% by weight of additives and from 5% to 40% by weight offiller, wherein the sum total of the components is always 100% byweight.

The additives preferably comprise antioxidants, antistats, blowingagents, further flame retardants, heat stabilizers, impact modifiers,processing aids, lubricants, light stabilizers, antidripping agents,compatibilizers, reinforcing agents, fillers, nucleus-forming agents,nucleating agents, additives for laser marking, hydrolysis stabilizers,chain extenders, color pigments, softeners, plasticizers and/orplasticizing agents.

Preference is given to a flame retardant containing 0.1 to 90% by weightof the monocarboxy-functionalized dialkylphosphinic acid, ester andsalts (III) and 0.1% to 50% by weight of further additives, morepreferably dials.

Preferred additives are also aluminum trihydrate, antimony oxide,brominated aromatic or cycloaliphatic hydrocarbons, phenols, ethers,chloroparaffin, hexachlorocyclopentadiene adducts, red phosphorus,melamine derivatives, melamine cyanurates, ammonium polyphosphates andmagnesium hydroxide. Preferred additives are also further flameretardants, more particularly salts of dialkylphosphinic acids.

More particularly, the present invention provides for the use of thepresent invention monocarboxy-functionalized dialkylphosphinic acid,esters and salts (III) as flame retardants or as an intermediate in themanufacture of flame retardants for thermoplastic polymers such aspolyesters, polystyrene or polyamide and for thermoset polymers such asunsaturated polyester resins, epoxy resins, polyurethanes or acrylates.

Suitable polyesters are derived from dicarboxylic acids and their estersand dials and/or from hydroxycarboxylic acids or the correspondinglactones. It is particularly preferable to use terephthalic acid andethylene glycol, 1,3-propanediol and 1,3-butanediol.

Suitable polyesters include inter alia polyethylene terephthalate,polybutylene terephthalate (Celanex® 2500, Celanex® 2002, from Celanese;Ultradur®, from BASF), poly-1,4-dimethylolcyclohexane terephthalate,polyhydroxybenzoates, and also block polyether esters derived frompolyethers having hydroxyl end groups; and also polyesters modified withpolycarbonates or MBS.

Synthetic linear polyesters having permanent flame retardancy arecomposed of dicarboxylic acid components, diol components of the presentinvention monocarboxy-functionalized dialkylphosphinic acids and ester,or of the monocarboxy-functionalized dialkylphosphinic acids and estersproduced by the method of the present invention as phosphorus-containingchain members. The phosphorus-containing chain members account for 2-20%by weight of the dicarboxylic acid component of the polyester. Theresulting phosphorus content in the polymer is preferably 0.1-5%, morepreferably 0.5-3% by weight.

The following steps can be carried out with or by addition of thecompounds produced according to the present invention.

Preferably, the molding material is produced from the free dicarboxylicacid and diols by initially esterifying directly and thenpolycondensing.

When proceeding from dicarboxylic esters, more particularly dimethylesters, it is preferable to first transesterify and then to polycondenseby using catalysts customary for this purpose.

Polyester production may preferably proceed by adding customaryadditives (crosslinking agents, matting agents and stabilizing agents,nucleating agents, dyes and fillers, etc) in addition to the customarycatalysts.

The esterification and/or transesterification involved in polyesterproduction is preferably carried out at temperatures of 100-300° C.,more preferably at 150-250° C.

The polycondensation involved in polyester production preferably takesplace at pressures between 0.1 to 1.5 mbar and temperatures of 150-450°C., more preferably at 200-300° C.

The flame-retardant polyester molding materials produced according tothe present invention are preferably used in polyester molded articles.

Preferred polyester molded articles are threads, fibers, self-supportingfilms/sheets and molded articles containing mainly terephthalic acid asdicarboxylic acid component and mainly ethylene glycol as diolcomponent.

The resulting phosphorus content in threads and fibers produced fromflame-retardant polyesters is preferably 0.1%-18%, more preferably0.5%-15% by weight and in the case of self-supporting films/sheets0.2%-15%, preferably 0.9%-12% by weight.

Suitable polystyrenes are polystyrene, poly(p-methylstyrene) and/orpoly(alpha-methylstyrene).

Suitable polystyrenes preferably comprise copolymers of styrene oralpha-methylstyrene with dienes or acrylic derivatives, for examplestyrene-butadiene, styrene-acrylonitrile, styrene-alkyl methacrylate,styrene-butadiene-alkyl acrylate and styrene-butadiene-alkylmethacrylate, styrene-maleic anhydride, styrene-acrylonitrile-methylacrylate; mixtures of high impact strength from styrene copolymers andanother polymer, for example a polyacrylate, a diene polymer or anethylene-propylene-diene terpolymer; also block copolymers of styrene,for example styrene-butadiene-styrene, styrene-isoprene-styrene,styrene-ethylene/butylene-styrene or styrene-ethylene/propylene-styrene.

Suitable polystyrenes preferably also comprise graft copolymers ofstyrene or alpha-methylstyrene, for example styrene on polybutadiene,styrene on polybutadiene-styrene or polybutadiene-acrylonitrilecopolymers, styrene and acrylonitrile (or methacrylonitrile) onpolybutadiene; styrene, acrylonitrile and methyl methacrylate onpolybutadiene; styrene and maleic anhydride on polybutadiene; styrene,acrylonitrile and maleic anhydride or maleimide on polybutadiene;styrene and maleimide on polybutadiene, styrene and alkyl acrylates oralkyl methacrylates on polybutadiene, styrene and acrylonitrile onethylene-propylene-diene terpolymers, styrene Wand acrylonitrile onpoly(alkyl acrylate)s or poly(alkyl methacrylate)s, styrene andacrylonitrile on acrylate-butadiene copolymers, and also their mixtures,as are also known for example as ABS, MBS, ASA or AES polymers.

The polymers preferably comprise polyamides and copolyamides derivedfrom diamines and dicarboxylic acids and/or from aminocarboxylic acidsor the corresponding lactams, such as nylon-2,12, nylon-4, nylon-4,6,nylon-6, nylon-6,6, nylon-6,9, nylon-6,10, nylon-6,12, nylon-6,66,nylon-7,7, nylon-8,8, nylon-9,9, nylon-10,9, nylon-10,10, nylon-11,nylon-12, and so on. Such polyamides are known for example under thetrade names Nylon®, from DuPont, Ultramid®, from BASF, Akulon® K122,from DSM, Zytel® 7301, from DuPont; Durethan® B 29, from Bayer andGrillamid®, from Ems Chemie.

Also suitable are aromatic polyamides proceeding from m-xylene, diamineand adipic acid; polyamides produced from hexamethylenediamine and iso-and/or terephthalic acid and optionally an elastomer as modifier, forexample poly-2,4,4-trimethylhexamethyleneterephthalamide orpoly-m-phenyleneisophthalamide, block copolymers of the aforementionedpolyamides with polyolefins, olefin copolymers, ionomers or chemicallybonded or grafted elastomers or with polyethers, for example withpolyethylene glycol, polypropylene glycol or polytetramethylene glycol.Also EPDM- or ABS-modified polyamides or copolyamides; and alsopolyamides condensed during processing (“RIM polyamide systems”).

The monocarboxy-functionalized dialkylphosphinic acid/ester/saltsproduced according to one or more of claims 1 to 13 are preferably usedin molding materials further used for producing polymeric moldedarticles,

It is particularly preferable for the flame-retardant molding materialto contain from 5% to 30% by weight of monocarboxy-functionalizeddialkylphosphinic acids, salts or esters produced according to one ormore of claims 1 to 13, from 5% to 90% by weight of polymer or mixturesthereof, from 5% to 40% by weight of additives and 5% to 40% by weightof filler, wherein the sum total of the components is always 100% byweight.

The present invention also provides flame retardants containingmonocarboxy-functionalized dialkylphosphinic acids, salts or estersproduced according to one or more of claims 1 to 13.

The present invention also provides polymeric molding materials and alsopolymeric molded articles, films, threads and fibers containing themonocarboxy-functionalized dialkylphosphinic acid salts (III) of themetals Mg, Ca, Al, Zn, Ti, Sn, Zr, Ce or Fe produced according to thepresent invention.

The examples which follow illustrate the invention.

Production, processing and testing of flame-retardant polymeric moldingmaterials and flame-retardant polymeric molded articles.

The flame-retardant components are mixed with the polymeric pellets andany additives and incorporated, on a twin-screw extruder (Leistritz LSM®30/34) at temperatures of 230 to 260° C. (glassfiber-reinforced PBT) orof 260 to 280° C. (glassfiber-reinforced PA 66). The homogenizedpolymeric strand was hauled off, water bath cooled and then pelletized.

After sufficient drying, the molding materials were processed on aninjection molding machine (Aarburg Allrounder) at melt temperatures of240 to 270° C. (glassfiber-reinforced PBT) or of 260 to 290° C.(glassfiber-reiforced PA 66) to give test specimens. The test specimensare subsequently flammability tested and classified using the UL 94(Underwriter Laboratories) test.

UL 94 (Underwriter Laboratories) fire classification was determined ontest specimens from each mixture, using test specimens 1.5 mm inthickness.

The UL 94 fire classifications are as follows:

V-0: Afterflame time never longer than 10 sec, total of afterflame timesfor 10 flame applications not more than 50 sec, no flaming drops, nocomplete consumption of the specimen, afterglow time for specimens neverlonger than 30 sec after end of flame application.V-1: Afterflame time never longer than 30 sec after end of flameapplication, total of afterflame time for 10 flame applications not morethan 250 sec, afterglow time for specimens never longer than 60 secafter end of flame application, other criteria as for V-0V-2: Cotton indicator ignited by flaming drops, other criteria as forV-1Not classifiable (ncl): does not comply with fire classification V-2.

Some investigated specimens were also tested for their LOI value. TheLOI (Limiting Oxygen Index) value is determined according to ISO 4589.According to ISO 4589, the LOI is the lowest oxygen concentration involume percent which in a mixture of oxygen and nitrogen will supportcombustion of the plastic. The higher the LOI value, the greater theflammability resistance of the material tested.

LOI 23 flammableLOI 24-28 potentially flammableLOI 29-35 flame resistantLOI >36 particularly flame-resistantChemicals and abbreviations used

-   VE water completely ion-free water-   AIBN azobis(isobutyronitrile), (from WAKO Chemicals GmbH)-   WakoV65 2,2′-azobis(2,4-dimethylvaleronitrile), (from WAKO Chemicals    GmbH)-   Deloxan® THP II metal scavenger (from Evonik Industries AG)

EXAMPLE 1

At room temperature, a three-neck flask equipped with stirrer andhigh-performance condenser is initially charged with 188 g of water andthis initial charge is devolatilized by stirring and passing nitrogenthrough it. Then, under nitrogen, 0.2 mg of palladium(II) sulfate and2.3 mg of tris(3-sulfophenyl)phosphine trisodium salt are added, themixture is stirred, and then 66 g of phosphinic acid in 66 g of waterare added. The reaction solution is transferred to a 2 l Büchi reactorand charged with ethylene under superatmospheric pressure while stirringand the reaction mixture is heated to 80° C. After 28 g of ethylene hasbeen taken up, the system is cooled down and free ethylene isdischarged. The reaction mixture is freed of solvent on a rotaryevaporator. The residue is admixed with 100 g of VE water and at roomtemperature stirred under nitrogen, then filtered and the filtrate isextracted with toluene, thereafter freed of solvent on a rotaryevaporator and the resulting ethylphosphonous acid [92 g (98% oftheory)] is collected.

EXAMPLE 2

Example 1 is repeated with 99 g of phosphinic acid, 396 g of butanol, 42g of ethylene, 6.9 mg of tris(dibenzylideneacetone)dipalladium, 9.5 mgof 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, followed bypurification over a column charged with Deloxan® THP II and the furtheraddition of n-butanol. At a reaction temperature of 80-110° C., thewater formed is removed by azeotropic distillation. The product ispurified by distillation at reduced pressure. Yield: 189 g (84% oftheory) of butyl ethylphosphonite.

EXAMPLE 3

Example 1 is repeated with 198 g of phosphinic acid, 198 g of water, 84g of ethylene, 6.1 mg of palladium(II) sulfate, 25.8 mg of9,9-dimethyl-4,5-bis(diphenylphosphino)-2,7-sulfonatoxanthene disodiumsalt, followed by purification over a column charged with Deloxan® THPII and the further addition of n-butanol. At a reaction temperature of80-110° C., the water formed is removed by azeotropic distillation. Theproduct is purified by distillation at reduced pressure. Yield: 374 g(83% of theory) of butyl ethylphosphonite.

EXAMPLE 4

A 500 ml five-neck flask equipped with gas inlet tube, thermometer,high-performance stirrer and reflux condenser with gas incineration ischarged with 94 g (1 mol) of ethylphosphonous acid (produced as inExample 1). Ethylene oxide is introduced at room temperature. A reactiontemperature of 70° C. is set with cooling, followed by further reactionat 80° C. for one hour. The ethylene oxide takeup is 65.7 g. The acidnumber of the product is less than 1 mg KOH/g. Yield: 129 g (94% oftheory) of 2-hydroxyethyl ethylphosphonite as colorless, water-clearproduct.

EXAMPLE 5

564 g (6 mol) of ethylphosphonous acid (produced as in Example 1) aredissolved in 860 g of water and initially charged to a 5 l five-neckflask equipped with thermometer, reflux condenser, high-performancestirrer and dropping funnel. The reaction mixture is heated to 100° C.and 406 g (7 mol) of allyl alcohol and 500 g of a 5% sodiumperoxodisulfate solution (1.5 mol % based on ally alcohol) is addeddropwise at atmospheric pressure over 1 h. Then, the water is distilledoff in vacuo, and the residue is taken up in THF and the insoluble saltsare filtered off. The solvent of the filtrate is removed in vacuo toleave 812 g (89% of theory) of ethyl-3-hydroxypropylphosphinic acid asoil.

EXAMPLE 6

94 g (1 mol) of ethylphosphonous acid (produced as in Example 1) and 114g (1 mol) of 2-methyl-2-propen-1-ol are initially charged in 200 ml ofglacial acetic acid in a four-neck round-bottom flask equipped withstirrer, reflux condenser, thermometer and nitrogen inlet and heated. Atabout 100° C., 98.4 g of a 5% solution of AIBN in glacial acetic acidare added dropwise over 1 h. Thereafter, the solvent was distilled offin vacuo to leave 153 g of ethyl-(2-methyl-3-hydroxypropyl) phosphinicacid.

EXAMPLE 7

A 1 l five-neck flask equipped with thermometer, reflux condenser,high-performance stirrer and dropping funnel was initially charged with447 g (3 mol) of butyl ethylphosphonite (produced as in Example 3) and168 g (3 mol) of 2-propenal. While stirring, 15 ml of sodium butoxide(30% strength in butanol) are added dropwise at such a rate that areaction temperature of max. 120° C. becomes established. The crudeproduct thus obtained is distilled in vacuo to obtain 550 g (89% oftheory) of butyl ethyl-(2-formylethyl)phosphinate as colorless liquid.

EXAMPLE 8

A 500 ml five-neck flask equipped with thermometer, reflux condenser,high-performance stirrer and dropping funnel is initially charged with63.5 g (0.46 mol) of 2-hydroxyethyl ethylphosphonite (produced as inExample 4) and 32.2 g (0.46 mol) of 2-methyl-2-propenal. While stirring,25 ml of sodium ethoxide (30% strength in ethanol) are added dropwise atsuch a rate that a reaction temperature of 60° C. becomes established. Aslightly yellow liquid is obtained. The crude product thus obtained isdistilled in vacuo. Yield: 84 g (88% of theory) of 2-hydroxyethylethyl-(2-methyl-2-formylethyl)phosphinate as colorless liquid.

EXAMPLE 9

A 1 L capacity loop reactor is filled with a mixture of 801 g (4.5 mol)of ethyl ethyl-(2-formylethyl)phosphinate (produced similarly to Example7) and 62 g (1.35 mol) of ethanol. The pump is switched on and per houra mixture of 726 g (6.00 mol) of ethyl ethylphosphonite and 336 g (6.00mol) of 2-propenal and also a solution of 16.8 g (0.20 mol) of potassiumethoxide in 120 g (2.61 mol) of ethanol are metered in while the coolingwater circuit is used to maintain the reaction mixture at a temperatureof about 40° C. The overflowing crude product is collected for 30 hoursand combined with the product going from the reactor to produce a totalamount of 35.5 kg. Following removal of the low boilers by distillationunder a water jet vacuum and filtration the product was vacuum distilledin a thin-film evaporator to obtain 30.0 kg (168.6 mol) of ethylethyl-(2-formylethyl)phosphinate. Minus the amount initially charged tothe reactor, this corresponds to a phosphorus yield of 93.8% at a rateof about 1000 g/l*h. A continuous production ofmono-2-formyl-functionalized dialkylphosphinic esters in good space-timeyields is possible in this way.

EXAMPLE 10

149 g (1 mol) of butyl ethylphosphonite (produced as in Example 2) and67 g (1.2 mol) of 2-propenal in 217 g of toluene are heated to about100° C. While stirring, 124 g of a 10% strength solution of WakoV65 intoluene are metered in. The solvent is distilled off in vacuo to obtain171 g (78% of theory) of butyl ethyl-(2-formylethyl)phosphinate.

EXAMPLE 11

15.2 g (0.1 mol) of ethyl-3-hydroxypropylphosphinic acid (produced as inExample 5) are dissolved in 150 ml of water and adjusted to pH 9 with 2NNaOH solution. Then, 0.45 g of charcoal with 5% Pt and 1% Bi is added,the suspension is heated to 70° C. and air is passed through thesuspension at 10 l/h. All the while, the pH of the suspension ismaintained at pH=9 by adding 2N NaOH in solution. After the reaction isended, the reaction solution is filtered to remove the catalyst, thefilter residue is washed and the water is distilled off in vacuo toobtain 19.5 g (93% of theory) of 3-(ethylhydroxyphosphinyl)propionicacid sodium salt as colorless solid.

EXAMPLE 12

15.2 g (0.1 mol) of ethyl-3-hydroxypropylphosphinic acid (produced as inExample 5) are dissolved in 150 ml of water and adjusted to pH 9 with 2NNaOH solution. Then, 0.45 g of charcoal with 5% Ft and 1% Bi is added,the suspension is heated to 70° C. and 30% strength hydrogenperoxidesolution is passed into the suspension at a flow rate of 1 molequivalent per hour while the pH of the suspension is maintained at pH=9by adding 2N NaOH solution. After the reaction is ended, the reactionsolution is filtered to remove the catalyst, the filter residue iswashed and the water is distilled off in vacuo to obtain 19.3 g (93% oftheory) of 3-(ethylhydroxyphosphinyl)propionic acid sodium salt(colorless solid).

EXAMPLE 13

20.6 g (0.1 mop of butyl ethyl-(2-formylethyl)phosphinate (produced asin Example 10) in 500 ml of acetone are mixed with 0.11 mol of Jonesreagent (12.7 g of chromium trioxide in 36.7 ml of water and 11.0 ml ofconcentrated sulfuric acid) at 0° C. by dropwise addition. The reactionmixture is additionally stirred for 3½ hours with ice cooling and 1 hourat room temperature. After 12 ml of isopropanol have been added, themixture is poured onto ice-water. Volatile constituents are subsequentlydistilled off in vacuo. The residue is taken up in tetrahydrofuran andextracted, Insoluble salts were filtered, off. The solvent of thefiltrate was removed in vacuo and the residue was recrystallized fromacetone to obtain 17.3 g (78% of theory) of3-(ethylbutoxyphosphinyl)propionic acid as oil,

EXAMPLE 14

In the aqueous solution of 420 g (2 mol) of3-(ethylhydroxyphosphinyl)propionic acid sodium salt (produced as inExample 12) is rendered acidic with about 196 g of concentrated sulfuricacid and the water is distilled off in vacuo. The residue was taken upin tetrahydrofuran and extracted. The insoluble salts were filtered off.The solvent of the filtrate was removed in vacuo and the residue wasrecrystallized from acetone to obtain 325 g (98% of theory) of3-(ethylhydroxyphosphinyl)-propionic acid as colorless solid.

EXAMPLE 15

444 g (2 mol) of 3-(ethylbutoxyphosphinyl)propionic acid (produced as inExample 13) are initially charged in a 1 l five-neck flask equipped withthermometer, reflux condenser, high-performance stirrer and droppingfunnel. At 160′C, during 4 h, 500 ml of water are metered in and abutanol-water mixture is distilled off. The solid residue isrecrystallized from acetone to obtain 309 g (93% of theory) of3-(ethylhydroxyphosphinyl)propionic acid as colorless solid.

EXAMPLE 16

996 g (6 mol) of 3-(ethylhydroxyphosphinyl)propionic acid (produced asin Example 14) are dissolved in 860 g of water and initially chargedinto a 5 l five-neck flask equipped with thermometer, reflux condenser,high-performance stirrer and dropping funnel and neutralized with about960 g (12 mol) of 50% sodium hydroxide solution. A mixture of 2583 g ofa 46% aqueous solution of Al₂(SO₄)₃.14 H₂O is added at 85° C. The solidmaterial obtained is subsequently filtered off, washed with hot waterand dried at 130° C. in vacuo. Yield: 1026 g (94% of theory) of3-(ethylhydroxyphosphinyl)propionic acid aluminum(III) salt as colorlesssalt.

EXAMPLE 17

222 g (1 mol) of 3-(ethylbutoxyphosphinyl)propionic acid (produced as inExample 13) and 85 g of titanium tetrabutoxide are refluxed in 500 ml oftoluene for 40 hours. The resulting butanol is distilled off from timeto time with proportions of toluene. The solution formed is subsequentlyfreed of solvent to leave 227 g of 3-(ethylbutoxyphosphinyl)propionicacid titanium salt.

EXAMPLE 18

498 g (3 mol) of 3-(ethylhydroxyphosphinyl)propionic acid (produced asin Example 14) are at 85° C. dissolved in 400 ml of toluene and admixedwith 888 g (12 mol) of butanol. At a reaction temperature of about 100°C., the water formed is removed by azeotropic distillation. The butyl3-(ethylbutoxyphosphinyl)propionate product is purified by distillationat reduced pressure.

EXAMPLE 19

540 g (3.0 mol) of 3-(ethylhydroxyphosphinyl)-2-methylpropionic acid(produced analogously to Example 13) are at 80° C. dissolved in 400 mlof toluene and admixed with 594 g (6.6 mol) of 1,4-butanediol andesterified at about 100° C. in a distillation apparatus equipped withwater trap during 4 h. On completion of the esterification the tolueneis removed in vacuo to leave 894 g (92% of theory) of 4-hydroxybutyl3-(ethyl-4-hydroxybutylphosphinyl)-2-methylpropionate as colorless oil.

EXAMPLE 20

To 276 g (1 mol) of butyl 3-(ethylbutoxyphosphinyl)propionate (producedas in Example 18) are added 155 g (2.5 mol) of ethylene glycol and 0.4 gof potassium titanyloxalate, followed by stirring at 200° C. for 2 h.Volatiles are distilled off by gradual evacuation to leave 244 g (98% oftheory) of 2-hydroxyethyl 3-(ethyl-2-hydroxyethoxyphosphinyl)propionate.

EXAMPLE 21

To 25.4 g of 2-hydroxyethyl3-(ethyl-2-hydroxyethoxyphosphinyl)propionate are added 290 g ofterephthalic acid, 188 g of ethylene glycol and 0.34 g of zinc acetate,and the mixture is heated to 200° C. for 2 h. Then, 0.29 g of trisodiumphosphate anhydrate and 0.14 g of antimony(III) oxide are added,followed by heating to 280° C. and subsequent evacuation. The meltobtained (357 g, phosphorus content 0.9%) is used to injection mold testspecimens 1.6 mm in thickness for measurement of the limiting oxygenindex (LOI) to ISO 4589-2 and also for the UL 94 (UnderwriterLaboratories) flammability test. The test specimens thus produced gavean LOI of 42% O₂ and were UL 94 classified as flammability class V-0.Corresponding test specimens without 2-hydroxyethyl3-(ethyl-2-hydroxyethoxyphosphinyl)propionate gave an LOI of just 31% O₂and were UL 94 classified as flammability class V-2 only. The polyestermolded article containing 2-hydroxyethyl3-(ethyl-2-hydroxyethoxyphosphinyl)propionate hence clearly hasflame-retardant properties.

EXAMPLE 22

To 15.2 g of 3-(ethylhydroxyphosphinyl)-2-methylpropionic acid (producedsimilarly to Example 13) are added to 12.9 g of 1,3-propylene glycol andat 160° C. the water formed by esterification is stripped off. Then, 378g of dimethyl terephthalate, 152 g of 1,3-propanediol, 0.22 g oftetrabutyl titanate and 0.05 g of lithium acetate are added, the mixtureis initially heated at 130 to 180° C. for 2 h with stirring andthereafter at 270° C. at underpressure. The polymer (438 g) contains0.6% of phosphorus, the LOI is 34.

EXAMPLE 23

To 14 g of 3-(ethylhydroxyphosphinyl)propionic acid (produced accordingto Example 14) are added 367 g of dimethyl terephthalate, 170 g of1,4-butanediol, 0.22 g of tetrabutyl titanate and 0.05 g of lithiumacetate, the mixture is initially heated at 130 to 180° C. for 2 h withstirring and thereafter at 270° C. at underpressure. The polymer (427 g)contains 0.6% of phosphorus, the LOI is 34, (untreated polybutyleneterephthalate: 23).

EXAMPLE 24

In a 250 ml five-neck flask equipped with reflux condenser, stirrer,thermometer and nitrogen inlet, 100 g of a bisphenol A bisglycidyl etherhaving an epoxy value of 0.55 mol/100 g (Beckopox EP 140, from Solutia)and 24.1 g (0.13 mol) of 3-(ethylhydroxyphosphinyl)-2-methylpropionicacid (produced similarly to Example 13) are heated to not more than 150°C. with stirring. A clear melt forms after 30 min. After a further hourof stirring at 150° C., the melt is cooled down and triturated to obtain118.5 g of a white powder having a phosphorus content of 3.3% by weight.

EXAMPLE 25

In a 2 L flask equipped with stirrer, water trap, thermometer, refluxcondenser and nitrogen inlet, 29.4 g of phthalic anhydride, 19.6 g ofmaleic anhydride, 24.8 g of propylene glycol, 18.7 g of 2-hydroxyethyl3-(ethyl-2-hydroxyethylphosphinyl)-propionate (produced as in Example20), 20 g of xylene and 50 mg of hydroquinone are heated to 100° C.while stirring and with nitrogen being passed through. The heatingoperation is stopped when the exothermic reaction is started. After thereaction has died down, stirring is continued at about 190° C. After 14g of water have been separated off, the xylene is distilled off and thepolymer melt is cooled down. This gives 91.5 g of a white powder havinga phosphorus content of 2.3% by weight.

EXAMPLE 26

A mixture of 50% by weight of polybutylene terephthalate, 20% by weightof 3-(ethylhydroxyphosphinyl)propionic acid aluminium(III) salt(produced as in Example 16) and 30% by weight of glass fibers arecompounded on a twin-screw extruder (Leistritz LSM 30/34) attemperatures of 230 to 260° C. to form a polymeric molding material. Thehomogenized polymeric strand was hauled off, water bath cooled and thenpelletized. After drying, the molding materials are processed on aninjection molding machine (Aarburg Allrounder) at 240 to 270° C. to formpolymeric molded articles which achieved a UL-94 classification of V-0.

EXAMPLE 27

A mixture of 53% by weight of nylon-6,6, 30% by weight of glass fibers,17% by weight of 3-(ethylbutoxyphosphinyl)propionic acid titanium salt(produced as in Example 17) are compounded on a twin-screw extruder(Leistritz LSM 30/34) to form polymeric molding materials. Thehomogenized polymeric strand was hauled off, water bath cooled and thenpelletized. After drying, the molding materials are processed on aninjection molding machine (Aarburg Allrounder) at 260 to 290° C. to formpolymeric molded articles which achieved a UL-94 classification of V-0.

1. A method for producing monocarboxy-functionalized dialkylphosphinicacids, esters or salts, comprising the steps of a) reacting a phosphinicacid source (I)

with olefins (IV)

in the presence of a catalyst A to form an alkylphosphonous acid, saltor ester (II)

b) reacting the alkyliphosphonous acid, salt or ester (II) with an allylalcohol (V) acrolein (V′), or both

in the presence of a catalyst B to form monofunctionalizeddialkylphosphinic acid derivative (VI), (VI′) or both

and c) reacting the monofunctionalized dialkylphosphinic acid derivative(VI), (VI′) or both with an oxidant or with an oxidant and water or inthe presence of a catalyst C with oxygen and water to formmonocarboxy-functionalized dialkylphosphinic acid derivative (III)

where R¹, R², R³, R⁴, R⁵, R⁶, R⁷ are identical or different and are eachindependently H, C₁-C₁₈-alkyl, C₆-C₁₈-aryl, C₆-C₁₈-aralkyl,C₆-C₁₈-alkylaryl CN, CHO, OC(O)CH₂CN, CH(OH)C₂H₅, CH₂CH(OH)CH₃,9-anthracene, 2-pyrrolidone, (CH₂)_(m)OH, (CH₂)_(m)NH₂, (CH₂)_(m)NCS,(CH₂)_(m)NC(S)NH₂, (CH₂)_(m)SH, (CH₂)_(m)S-2-thiazoline, (CH₂)_(m)SiMe₃,C(O)R⁸, (CH₂)_(m)C(O)R⁸, CH═CH—R⁸, CH═CH—C(O)R⁸ and where R⁸C₁-C₈-alkylor C₆-C₁₈-aryl and m is an integer from 0 to 10 and X and Y is areidentical or different and are each independently H, C₁-C₁₈-alkyl,C₆-C₁₈-aryl, C₆-C₁₈-aralkyl, C₆-C₁₈-alkylaryl, (CH₂)_(k)OH,CH₂—CHOH—CH₂OH, (CH₂)_(k)O(CH₂)_(k)H, (CH₂)_(k)—CH(OH)—(CH₂)_(k)H,(CH₂—CH₂O)_(k)H, (CH₂—C[CH₃]HO)_(k)H, (CH₂—C[CH₃]HO)_(k)(CH₂—CH₂O)_(k)H,(CH₂—CH₂O)_(k)(CH₂—C[CH₃]HO)H, (CH₂—CH₂O)_(k)-alkyl,(CH₂—C[CH₃]HO)_(k)-alkyl, (CH₂—C[CH₃]HO)_(k)(CH₂—CH₂O)_(k)-alkyl,(CH₂—CH₂O)_(k)(CH₂—C[CH₃]HO)O-alkyl, (CH₂)_(k)—CH═CH(CH₂)_(k)H,(CH₂)_(k)NH₂, (CH₂)_(k)N[(CH₂)_(k)H]₂, where k is an integer from 0 to10, Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Cu, Ni, Li,Na, K, H, a protonated nitrogen base and the catalysts A and C comprisetransition metals, transition metal compounds, or catalyst systemscomposed of a transition metal, transition metal compound and at leastone ligand or a combination thereof, and the catalyst B comprisesperoxide-forming compounds, peroxo compounds, comprises azo compounds,alkali metals, alkaline earth metals, hydrides, alkoxides or acombination here.
 2. The method according to claim 1 wherein themonocarboxy-functionalized dialkylphosphinic acid, its salt or ester(III) obtained after step c) is subsequently reacted in a step d) withmetal compounds of Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr,Mn, Li, Na, K and/or a protonated nitrogen base to formmonocarboxy-functionalized dialkylphosphinic acid salts (III) of thesemetals and/or of a nitrogen compound.
 3. The method according to claim 1wherein the alkylphosphonous acid, salt or ester (II) obtained afterstep a) and/or the monofunctionalized dialkylphosphinic acid, salt orester (VI) and/or (VI′) obtained after step b) and/or themonocarboxy-functionalized dialkylphosphinic acid, salt or ester (III)obtained after step c) and/or the particular resulting reaction solutionthereof are esterified with an alkylene oxide or an alcohol M-OH, M′-OHor both, and the resulting alkylphosphonous ester (II),monofunctionalized dialkylphosphinic ester (VI) and/or (VI′), and/ormonocarboxy-functionalized dialkylphosphinic ester (III) are subjectedto reaction steps b), c) or d).
 4. The method according to claim 1,wherein the groups C₆-C₁₈-aryl, C₆-C₁₈-aralkyl and C₆-C₁₈-alkylaryl aresubstituted with SO₃X₂, —C(O)CH₃, OH, CH₂OH, CH₃SO₃X₂, PO₃X₂, NH₂, NO₂,OCH₃, SH, OC(O)CH₃ or a combination thereof.
 5. The method according toclaim 1, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷ are identical or differentand are each independently H, methyl, ethyl, n-propyl, isopropyl,n-butyl, isobutyl, tert-butyl, phenyl or a combination thereof.
 6. Themethod according to claim 1, wherein X and Y are identical or differentand are each H, Ca, Mg, Al, Zn, Ti, Fe, Ce, methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, ethylene glycol,propyl glycol, butyl glycol, pentyl glycol, hexyl glycol, allyl,glycerol or a combination thereof.
 7. The method according to claim 1,wherein the transition metals, transition metal compounds or both arefrom the first, seventh and eighth transition groups.
 8. The methodaccording to claim 1, wherein the transition metals, transition metalcompounds or both contain rhodium, nickel, palladium, platinum,ruthenium, gold or a combination thereof.
 9. The method according toclaim 1, wherein the catalyst B is hydrogen peroxide, sodium peroxide,lithium peroxide, potassium persulfate, sodium persulfate, ammoniumpersulfate, sodium peroxodisulfate, potassium peroxoborate, peraceticacid, benzoyl peroxide, di-t-butyl peroxide peroxodisulfuric acid,azobisisobutyronitrile, 2,2′-azobis(2-amidinopropane) dihydrochloride,2,2′azobis(N,N′dimethyleneisobutyramidine) dihydrochloricle, lithium,lithium hydride, lithium aluminum hydride, methyllithium, butyllithium,t-butyllithium, lithium diisopropylamide, sodium, sodium hydride, sodiumborohydride, sodium methoxide, sodium ethoxide, sodium butoxide,potassium methoxide, potassium ethoxide an potassium butoxide or acombination thereof.
 10. The method according to claim 1 wherein theoxidizing agents are potassium permanganate, manganese oxide, chromiumtrioxide, potassium dichromate, pyridine dichromate, pyridinechlorochromate, Collins reagent, Jones reagent, Corey-Gilman-Ganemreagent, (Dess-Martin) periodinane, o-iodoxybenzoic acid, rutheniumtetroxide, ruthenium dioxide, tetra-n-propyl perruthenate, rutheniumtrichloride/sodium periodate, ruthenium dioxide/sodium periodate,chlorine, hypochlorite or peroxo compounds.
 11. The method according toclaim 1, wherein the allyl alcohol derivatives (V) are 2-propen-1-ol,2-methyl-2-propen-1-ol, 2-isobutyl-2-propen-1-ol,2-(trimethylsilyl)-2-propen-1-ol, 3-phenyl-2-propen-1-ol,3-(trimethylsilyl)-2-propen-1-ol,3-(4-hydroxy-3-methoxyphenyl)-2-propen-1-ol,2-methyl-3-phenyl-2-propen-1-ol, 2-buten-1-ol, 2-methyl-2-buten-1-ol,3-(trimethylsilyl)-2-buten-1-ol, 3-methyl-2-buten-1-ol,3-phenyl-2-buten-1-ol, 3 (trimethylsilyl)-2-buten-1-ol,2-methyl-3-phenyl-2-buten-1-ol, 2-penten-1-ol, 2-methyl-2-penten-1-ol,2-(trimethylsilyl)-2-penten-1-ol, 3-methyl-2-penten-1-ol,3-phenyl-2-penten-1-ol, 4-methyl-2-penten-1-ol, 4 phenyl-2-penten-1-olor a combination thereof.
 12. The method according to one claim 1,wherein the acrolein derivatives (V′) are 2-propenal,2-methyl-2-propenal, 2-phenyl-2-propenal, 3-phenyl-2-propenal,2-methyl-3-phenyl-2-propenal, 2-butenal, 2-methyl-2-butenal,2-phenyl-2-butenal, 3-methyl-2-butenal, 2-methyl-2-butenal, 2-pentenal,2-methyl-2-pentenal, 2-phenyl-2-pentenal, 4-methyl-2-phenyl-2-pentenal,2 2-dimethyl-4-pentenal or a combination thereof.
 13. The methodaccording claim 1, wherein the alcohol of the general formula M-OH islinear or branched, saturated and unsaturated, monohydric organicalcohols having a carbon chain length of C₁-C₁₈ and the alcohol of thegeneral formula M′-OH is linear or branched, saturated and unsaturatedpolyhydric organic alcohols having a carbon chain length of C₁-C₁₈. 14.A composition comprising monocarboxy-functionalized dialkylphosphinicacids, esters or salts obtained according to claim 1, wherein thecomposition is in the form of an intermediate for further syntheses, abinder, a crosslinker or accelerant to cure epoxy resins, polyurethanesand unsaturated polyester resins, polymer stabilizers, crop protectionagents, a therapeutic or additive in therapeutics for humans andanimals, a sequestrant, a mineral oil additive, a corrosion controlagent, washing and cleaning compositions or in electronic compositions.15. A composition comprising monocarboxy-functionalizeddialkylphosphinic acids, salts or esters obtained according to claim 1,wherein the composition is in the form of a flame retardant, a flameretardant for clearcoats and intumescent coatings, as a flame retardantfor wood and other cellulosic products, a reactive flame retardant forpolymers a nonreactive flame retardant for polymers, flame-retardantpolymeric molding materials, flame-retardant polymeric molded articlesor a flame-retardant finishing composition for polyester and cellulosestraight and blend fabrics by impregnation.
 16. A flame-retardantthermoplastic or thermoset polymeric molding material containing 0.5% to45% by weight of monocarboxy-functionalized dialkylphosphinic acids,salts or esters obtained according to claim 1, 0.5% to 95% by weight ofthermoplastic or thermoset polymer or mixtures thereof, 0% to 55% byweight of additives and 0% to 55% by weight of filler or reinforcingmaterials, wherein the sum total of the components is 100% by weight.17. Flame-retardant thermoplastic or thermoset polymeric moldedarticles, films, threads and or fibers containing 0,5% to 45% by weightof monocarboxy-functionalized dialkylphosphinic acids, salts or estersobtained according to claim 1, 0.5% to 95% by weight of thermoplastic orthermoset polymer or mixtures thereof, 0% to 55% by weight of additivesand 0% to 55% by weight of filler or reinforcing materials, wherein thesum total of the components is 100% by weight.